TW201629151A - Polymer resin composition having excellent flame retardancy - Google Patents

Abstract

The present invention relates to a polymer resin composition, and more specifically to a polymer resin composition having excellent chemical resistance and flame retardancy even while exhibiting improved physical properties such as heat resistance and impact resistance.

Description

Polymer resin composition having excellent flame retardancy

The present invention relates to a polymer resin composition, and more particularly to a polymer resin composition which has excellent chemical resistance and flame retardancy while exhibiting preferable physical properties such as heat resistance and impact resistance.

The polyester resin has relatively excellent heat resistance, mechanical strength, and elastic strength. Therefore, polyester resins are widely used as reinforced plastics, coatings, films, molding resins, and the like. Due to the special physical properties of polyester resins, polyester resins have recently been used more and more in the fields of interior building materials or molding signboards.

However, compared to other polymeric materials such as acrylic materials and polycarbonate-based materials, polyester resins have lower heat resistance, and polyester resins may be Physical properties are degraded or deformed due to changes in the surrounding environment. Therefore, the polyester resin has a problem that it is not suitable for use alone in an exterior exterior material or an automobile part.

In addition, polycarbonate resin is a synthetic resin having impact resistance or heat resistance, and has been used in various fields, including appearances, packaging materials, boxes of various building materials and electronic products. Box or exterior or interior material used for interior design. Polycarbonate resins have many demands due to their good mechanical properties, but they still have problems. The appearance or color of polycarbonate may be due to various detergents and female cosmetics frequently used in the home environment. ), children's hand sanitizer, etc. change or crack, and its products are degraded by a variety of chemicals used in daily life.

There are a number of implemented solutions to solve the problems encountered with the above polyester resins or polycarbonate resins. In addition, research on a method of mixing a polyester resin with a polycarbonate resin has also begun.

In particular, for use in electrical or electronic products and office supplies that generate heat during use, such as displays or facsimile machines, or materials that are fragile to the environment (e.g., fire), the resin composition should be flame retardant. However, both polyester resins and polycarbonate resins have flammability characteristics. Further, since the polyester resin and the polycarbonate resin have different melt viscosities and molecular structures from each other, there is a limitation in merely mixing the two to increase the flame retardancy.

Therefore, a flame retardant is generally used to impart flame retardancy to the resin composition. However, when a high level of flame retardant is used to obtain a high degree of flame retardancy, there is a disadvantage that the flame retardant may be eluted, and physical properties such as impact strength, elastic strength and transparency may be remarkably The reduction, especially the heat resistance, will drop dramatically.

In addition, various methods have been proposed to increase the chemical resistance of polycarbonate while maintaining its mechanical properties, especially heat resistance. However, the degree of improvement in heat resistance is not sufficient to be applied to practical industries, and the appearance characteristics of the produced resin product are also deteriorated. Further, attempts have been made to additionally blend a polycarbonate resin with one or more additional materials to simultaneously increase heat resistance and chemical resistance, but it is difficult to achieve an appropriate degree of chemical resistance.

Therefore, for polyester resins and polycarbonate resins, it is still necessary to study a polymer resin composition having excellent chemical resistance and flame retardancy while maintaining complementary physical properties such as strength, transparency, heat resistance, and the like. .

The present application claims priority to Korean Patent Application No. 10-2014-0183431, filed on Dec.

technical problem

An object of the present invention is to provide a polymer resin composition which has excellent chemical resistance and flame retardancy while exhibiting excellent mechanical and physical properties such as strength, transparency and heat resistance, and includes a specific composition. One of a polyester resin, a polycarbonate resin and a flame retardant.

Technical solution

In order to achieve the above object, the present invention provides a polymer resin composition comprising 5 to 70% by weight of one of a polyester resin, 15 to 65% by weight of one of polycarbonate resins, and 1 to 20% by weight of one of flame retardants . The polyester resin comprises a residue of a dicarboxylic acid component and a residue of a glycol component, wherein the residue of the dicarboxylic acid component comprises terephthalic acid, and the residue of the glycol component comprises 5 to 60 mole percent (mol%) isosorbide, 5 to 80 mole percent cyclohexane dimethanol, and the remaining content of other glycol compounds.

According to an embodiment of the present invention, the above polyester resin may have a weight average molecular weight of from about 10,000 to about 100,000 g/mol and a glass transition temperature of from about 0 to about 200 °C ( Glass transition temperature). The above polycarbonate resin may have a weight average molecular weight of from about 10,000 to about 100,000 g/mol and a glass transition temperature of from about 50 to about 200 °C.

Further, the dicarboxylic acid component in the polyester resin may comprise one or more selected from the group consisting of an aromatic dicarboxylic acid having 8 to 20 carbon atoms and an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. A group of acidic dicarboxylic acids. The glycol component in the polyester resin may comprise one or more groups selected from the group consisting of compounds represented by the following Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3:

Chemical formula 1

In Chemical Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, and n ₁ And n ₂ are each independently an integer of 0 to 3.

Chemical formula 2

In Chemical Formula 2, each of R ₅ , R ₆ , R ₇ and R _{8 is} each independently hydrogen or an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms.

Chemical formula 3

In Chemical Formula 3, n ₃ is an integer of 1 to 7.

Furthermore, the above flame retardant may comprise one or more selected from the group consisting of a halogen-based flame retardant, a phosphorus-based flame retardant, and an inorganic flame retardant. ) the group consisting of.

According to another embodiment of the present invention, the above polymer resin composition may further comprise one or more copolymers selected from the group consisting of aromatic vinyl-unsaturated nitrile copolymers, Unsaturated nitrile-diene-based rubber-aromatic vinyl graft copolymer, alkyl methacrylate-diene rubber-aromatic vinyl graft copolymerization A group consisting of an alkyl methacrylate-diene-based rubber-aromatic vinyl graft copolymer and an alkyl methacrylate-silicon-alkyl acrylate graft copolymer.

In this case, it is selected from the group consisting of an aromatic vinyl-unsaturated nitrile copolymer, an unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-diene rubber-aromatic vinyl The one or more copolymers of the group of the graft copolymer and the monoalkyl methacrylate-ruthenium-alkyl acrylate graft copolymer may be included in an amount of from about 1 to about 25% by weight.

Further, the diene-based rubber may be a butadiene type rubber or an isoprene-type rubber. The unsaturated nitrile may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and alpha-chloroacrylonitrile. a group consisting of (α-chloroacrylonitrile). The aromatic vinyl may be one or more selected from the group consisting of styrene, α-methyl styrene vinyl toluene, t-butyl styrene, Halogen-substituted styrene, 1,3-dimethyl styrene, 2,4-dimethyl styrene and B A group consisting of ethyl styrene.

According to an embodiment of the present invention, the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer. The alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer may be a methyl methacrylate-butadiene-styrene graft copolymer. The alkyl methacrylate-ruthenium-alkyl acrylate graft copolymer may preferably be a methyl methacrylate-silicon-butyl acrylate graft copolymer.

According to another embodiment of the present invention, the above polymer resin composition has a tensile strength loss defined by the following formula 1 in the range of from about 0.5 to about 20%, and Formula 1 is:

Tensile strength loss (%) = [(tensile strength before test - tensile strength after test) / tensile strength before test] x 100.

Further, when a 3.0 mm polymer resin composition is supplied to the UL94 V test (vertical burning test), the polymer resin composition may have flame retardancy higher than or equal to the V-0 level.

Furthermore, the polymer resin composition may further comprise one or more additives selected from the group consisting of dyes, pigments, impact modifiers, fillers, stabilizers ( Stabilizer), lubricant, antioxidant, antimicrobial agent, releasing agent, anti-hydrolysis agent, plasticizer, nucleating agent A group consisting of a nucleating agent, an organic-inorganic particle, or a mixture of the above.

Beneficial effect

As described above, the polymer resin composition of the present invention has excellent flame retardancy while exhibiting preferable physical properties such as strength, transparency and heat resistance.

The polymer resin composition of the present invention comprises 5 to 70% by weight of one of the polyester resin, 15 to 65% by weight of one of the polycarbonate resin and 1 to 20% by weight of one of the flame retardants. The polyester resin contains a residue of a dicarboxylic acid component and a residue of a glycol component. The residue of the dicarboxylic acid component includes terephthalic acid, and the residue of the glycol component contains 5 to 60 mole percent (mol%) of isosorbide, 5 to 80 mole percent of cyclohexanedimethanol, and the remainder The content of other glycol compounds.

The terminology used herein is for the purpose of illustration and description, and, The singular forms used are also intended to include the plural unless otherwise indicated. The words "including, including or having" in the specification are intended to indicate the existence of the features, shapes, steps, essential elements or combinations thereof, but it must be understood that one or The possibility of a plurality of other features, shapes, steps, essential elements or combinations thereof.

The invention may be embodied in a variety of variations and various modifications, and specific specific examples are provided and described in detail below. However, it is to be understood that the invention is not intended to be limited to the details of the invention.

Hereinafter, the present invention will be described in detail.

According to an embodiment of the present invention, there is provided a polymer resin composition comprising 5 to 70% by weight of a polyester resin, 15 to 65% by weight of a polycarbonate resin and 1 to 20% by weight of a flame retardant. The polyester resin contains a residue of a dicarboxylic acid component and a residue of a glycol component. The residue of the dicarboxylic acid component includes terephthalic acid, and the residue of the glycol component contains 5 to 60 mole percent of isosorbide, 5 to 80 mole percent of cyclohexane dimethanol, and the balance of the other two. Alkoxide compound.

As described above, in order to supplement or enhance the physical properties of the polyester resin, a method of mixing a specific polymer resin has been proposed, but the effect of the improvement by the mixing of these components and the complementary synergistic effect have limitations. Moreover, it is difficult to maintain sufficient mechanical properties and flame retardancy.

Therefore, the present inventors conducted thorough research on a polymer resin composition to exhibit excellent mechanical properties and flame retardancy, and can be applied to various electric or electronic components, office supplies, automobile parts, and daily necessities. , building components, etc. It has been found through experiments that when polyester resin, polycarbonate resin and flame retardant are mixed in a specific combination ratio, excellent flame retardancy can be obtained while having excellent physical properties (for example, impact resistance and heat resistance). Polymer resin composition. The present invention has been completed based on this finding.

The polymer resin composition can be produced by using a conventional method and apparatus (for example, a blend or mixture for preparing a polymer resin), and is not particularly limited. For example, a polycarbonate resin, a polyester resin, and a flame retardant may be added to a conventional blender, mixer, or tumbler, and then passed through a double-screw kneading extruder (twin). -screw kneading extruder) is mixed to provide a polymer resin composition. In the method of preparing a polymer resin composition, each resin is preferably used in a sufficiently dry state.

Further, in the polymer resin composition of one embodiment of the present invention, the polyester resin contains a residue of a dicarboxylic acid component and a residue of a glycol component. The residue of the dicarboxylic acid component includes terephthalic acid, and the residue of the glycol component contains 5 to 60 mole percent of isosorbide, 5 to 80 mole percent of cyclohexane dimethanol, and the balance of the other two. Alkoxide compound.

The term "residue" as used herein, refers to a specific moiety or unit derived from a particular compound and which is included in the product of the chemical reaction when a particular compound is involved in a chemical reaction. For example, the "residue" of a dicarboxylic acid component or the "residue" of a glycol component respectively means a polyester formed by esterification or polycondensation. a group derived from a carboxylic acid component or a glycol component.

The term "dicarboxylic acid component" as used herein is intended to include dicarboxylic acids such as terephthalic acid, alkyl esters thereof (lower alkyl esters having 1 to 4 carbon atoms, for example) Monomethyl ester, monoethyl ester, dimethyl ester, diethyl ester or dibutyl ester, and/or An acid anhydride or the like can be reacted with a glycol component to produce a dicarboxylic acid moiety such as a terephthaloyl moiety.

Since the dicarboxylic acid component for synthesizing polyester includes terephthalic acid, the produced polyester resin has preferable physical properties such as heat resistance, chemical resistance or flame retardancy.

Further, in addition to terephthalic acid, the dicarboxylic acid component in the polyester resin may further comprise one or more selected from the group consisting of aromatic dicarboxylic acids having 8 to 20 carbon atoms and having 4 A group consisting of aliphatic dicarboxylic acids of up to 20 carbon atoms.

The aromatic dicarboxylic acid component may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and preferably has 8 to 14 carbon atoms, or a mixture of the above. Examples of the aromatic dicarboxylic acid may include isophthalic acid, naphthalene dicarboxylic acid such as 2,6-naphthalene dicarboxylic acid, and biphenyldicarboxylate. Diphenyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 2,5-furan dicarboxylic acid, 2, Although it is a 5-thiophene dicarboxylic acid etc., it is not limited to the specific example of an aromatic dicarboxylic acid.

The aliphatic dicarboxylic acid may be an aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and preferably has 4 to 12 carbon atoms, or a mixture of the above. Examples of the aliphatic dicarboxylic acid may include a linear, branched or cyclic aliphatic dicarboxylic acid component, for example, cyclohexane dicarboxylic acid such as 1,4. - 1,4-cyclohexane dicarboxylic acid and 1,3-cyclohexane dicarboxylic acid, phthalic acid, azelaic acid ( Sebacic acid), succinic acid, isodecyl succinic acid, maleic acid, fumaric acid, adipic acid, glutaric acid Glutaric acid), azelaic acid, etc., but specific examples of the aliphatic dicarboxylic acid are not limited thereto.

Further, the above dicarboxylic acid component may comprise from about 50 to about 100 mole percent, preferably from about 70 to about 100 mole percent terephthalic acid, and from about 0 to about 50 mole percent, preferably about 0 to about 30 mole percent of one or more dicarboxylic acids selected from the group consisting of aromatic dicarboxylic acids and aliphatic dicarboxylic acids. When the proportion of terephthalic acid in the dicarboxylic acid component is too low or too high, the physical properties of the polyester resin such as heat resistance, chemical resistance, weatherability, and the like may be deteriorated.

Further, the glycol component used in the synthesis of the polyester may include 5 to 60 mole percent of isosorbide, 5 to 80 mole percent of cyclohexanedimethanol, and the balance of other glycol compounds.

Since the glycol component includes isosorbide (1,4:3,6-dianhydroglucitol), the polyester resin produced not only has better heat resistance but also has better physical properties such as chemical resistance and Drug resistance. Since the content of cyclohexanedimethanol (for example, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol) in the glycol component is increased, the yield is The impact resistance of the polyester resin is also greatly improved.

On the other hand, in addition to isosorbide and cyclohexanedimethanol, the glycol component may additionally include other glycol components. The term "other glycol component" means a glycol component other than isosorbide and cyclohexanedimethanol, and examples thereof may include an aliphatic diol and an aromatic diol (aromatic) Diol) or a mixture of the two.

Further, the glycol component in the polyester resin may include one or more groups selected from the group consisting of the compounds represented by the following Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3:

Chemical formula 1

In Chemical Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, and n ₁ And n ₂ are each independently an integer of 0 to 3.

Chemical formula 2

In Chemical Formula 2, each of R ₅ , R ₆ , R ₇ and R _{8 is} each independently hydrogen or an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms.

Chemical formula 3

In Chemical Formula 3, n ₃ is an integer of 1 to 7.

The polyester resin may preferably have a weight average molecular weight of from about 10,000 to about 100,000 g/mol and a glass transition temperature of from about 0 to about 200 °C.

The polyester resin accounts for 5 to 70% by weight, preferably about 10 to about 70% by weight, more preferably about 20 to about 60% by weight, based on the total mass of the resin composition. When the content of the polyester resin is less than a specific range, there may be a problem that chemical resistance is lowered and tensile strength loss is increased. When the content of the polyester resin is higher than a specific range, there may be a problem that heat resistance is lowered.

On the other hand, the above polyester resin may be provided by a method of preparing a polyester resin, the method comprising the steps of: esterifying a glycol component with a dicarboxylic acid component, wherein the glycol component comprises 5 to 60 moles a percentage of isosorbide, 5 to 80 mole percent of cyclohexanedimethanol, and the balance of other glycol compounds, the dicarboxylic acid component is terephthalic acid; when the esterification has been carried out 80% or more, Adding a phosphorous-based stabilizer to the reaction solution; and polycondensing the esterified reaction product.

According to the method of preparing a polyester resin, a zinc-based compound is used as a reaction catalyst for esterification, and a phosphorus-based stabilizer is added to the reaction solution at the end of the esterification. For example, when the esterification has been carried out by 80% or more, the esterification reaction product is polycondensed, thereby providing physical properties having, for example, high heat resistance, high flame retardancy, and high impact resistance, and A polyester resin having good appearance properties, high transparency, and good formability.

Details regarding the dicarboxylic acid component including terephthalic acid, cyclohexanedimethanol, isosorbide, and other glycol compounds are the same as those described above.

Specific examples of the zinc-based catalyst may include zinc acetate, zinc acetate dehydrate or a mixture of the above. Specific examples of the phosphorus-based stabilizer may include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonium acetate (triethyl phosphate) Triethyl phosphonoacetate) or a mixture of two or more of the above materials.

The esterification step can carry out the reaction of the dicarboxylic acid component with the glycol component at a pressure of from about 0 to about 10.0 kg/cm 2 and at a temperature of from about 150 to about 300 ° C. The conditions for the esterification can be appropriately controlled depending on the specific properties of the polyester to be produced, the molar ratio between the dicarboxylic acid component and the glycol, or the process conditions. Specifically, the esterification is preferably from about 0 to about 5.0 kg/cm 2 , more preferably from about 0.1 to about 3.0 kg/cm 2 , and more preferably from about 200 to about 270 ° C, more preferably It is carried out at a temperature of from about 240 to about 260 °C.

Further, the esterification may be carried out in a batch or continuous manner, and each of the raw materials may be introduced separately or, preferably, in a slurry form, a mixture of the glycol component and the dicarboxylic acid component. Further, the glycol component which is solid at room temperature may be dissolved in water or ethylene glycol, and then mixed with a dicarboxylic acid component such as terephthalic acid to form a slurry. Alternatively, the isosorbide may be melted at a temperature of 60 ° C or higher and then mixed with a dicarboxylic acid component such as terephthalic acid and other glycol components to form a slurry. Further, water may be added to a slurry in which a dicarboxylic acid component and a copolymer of a glycol component such as isosorbide and ethylene glycol are mixed, thereby improving the fluidity of the slurry.

The molar ratio of the dicarboxylic acid component to the glycol component used for the esterification may range from about 1:1.05 to 1:3.0. If the molar ratio between the dicarboxylic acid component and the glycol component is less than about 1.05, the unreacted dicarboxylic acid component may remain in the polymerization and cause deterioration of the transparency of the resin. Further, if the molar ratio exceeds about 3.0, the polymerization rate may be lowered or the productivity of the resin may be degraded.

The polycondensation of the esterification reaction product can include the following steps. The esterification reaction product of the dicarboxylic acid component is reacted with the glycol compound at a temperature of from about 150 to about 300 ° C and a reduced pressure of from about 600 to about 0.01 mmHg for about 1 to about 24 hours.

The polycondensation may be at a temperature of from about 150 ° C to about 300 ° C, preferably from about 200 ° C to about 290 ° C, more preferably from about 260 ° C to about 280 ° C, and from about 600 to about 0.01 mm Hg, preferably about It is carried out under reduced pressure of from 200 to about 0.05 mmHg, more preferably from about 100 to about 0.1 mmHg. In polycondensation applications where reduced pressure conditions are employed, by-products of the polycondensation reaction, such as ethylene glycol, can be removed outside the system. Therefore, if the polycondensation is carried out under a reduced pressure condition other than about 400 to 0.01 mmHg, by-products cannot be sufficiently excluded.

Further, if the polycondensation is carried out outside the temperature range of from 150 ° C to 300 ° C, for example, if the temperature at which the polycondensation is carried out is 150 ° C or less, it may be difficult to form a by-product of polycondensation (for example, ethylene glycol). It is removed to the outside of the system, so the intrinsic viscosity of the final product becomes low, and the physical properties of the produced polyester resin are also degraded. If the temperature at which the polycondensation is carried out is higher than 300 ° C, the appearance of the obtained polyester resin has a high probability of yellowing. In addition, the time during which the polycondensation is carried out may depend on whether the intrinsic viscosity of the final product to be obtained is to an appropriate degree, for example, an average residence time of from 1 to 24 hours.

On the other hand, the preparation method of the polyester resin component may further include a step of adding a polycondensation catalyst. The polycondensation catalyst may be added to the esterified or transesterified product before the start of polycondensation, or may be added to a mixed slurry comprising a glycol component and a dicarboxylic acid component prior to esterification, or may be added during esterification.

Titanium-based compounds, germanium-based compounds, antimony-based compounds, aluminum-based compounds, tin-based compounds, and A mixture of the above materials can be used as the above polycondensation catalyst.

Examples of the titanium-based compound may include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, and polytetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate, tetrabutyl titanate Polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate, triethanolamine titanate (triethanolamine titanate), acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, Titanium dioxide/silicon dioxide copolymer, titanium dioxide/zirconium dioxide copolymer, and the like.

Examples of the mercapto compound may include germanium dioxide (GeO ₂ ), germanium tetrachloride (GeCl ₄ ), germanium ethyleneglycoxide, germanium acetate, and copolymerization of the above compounds. Or a mixture of the above compounds. Preferably, cerium oxide may be used, or crystalline or amorphous cerium oxide may be used, or cerium oxide soluble in ethylene glycol may be used.

On the other hand, the polycarbonate resin is blended with the polyester resin, whereby the mechanical properties of the resin composition, such as impact strength, tensile strength and elongation, can be improved. And heat resistance can be greatly improved.

As the polycarbonate-based polymer, a polycarbonate-based polymer produced by using bisphenol-A as a basic constituent material can be used variously. Specifically, the polycarbonate-based polymer having different molecular weights and physical properties is not particularly limited in consideration of the properties of the resin molded article produced. For example, polycarbonate-based polymers having a weight average molecular weight of from about 10,000 to about 100,000 g/mol and a glass transition temperature of from about 50 to about 200 °C are preferably used.

The above polycarbonate resin may be contained in an amount of 15 to 65% by weight, preferably about 20 to about 60% by weight, based on the total mass of the resin composition. If the content of the polycarbonate resin is less than the above specific range, the effect of improving mechanical properties such as strength, elongation, and heat resistance may be small. If the content of the polycarbonate resin exceeds a specific weight part, the chemical resistance, processing characteristics and flame retardancy of the produced resin or formed body may be lowered.

On the other hand, the above flame retardant is mixed with a polyester resin and a polycarbonate resin, thereby helping to improve the flame retardancy of the entire resin composition.

According to an embodiment of the present invention, the flame retardant usable herein includes a halogen-based flame retardant, a phosphorus-based flame retardant, and an inorganic flame retardant. Retardant) or a mixture of the above flame retardants.

Specific examples of the halogen-based flame retardant may include decabromodiphenyl ether (DECA), tetrabromo-bisphenol A (TBBA), 1,2-bispentabromophenylethane (1, 2). -bis(pentabromophenyl)ethane, octabromotrimethylphenyl indane, brominated epoxy oligomer, and the like.

Examples of the phosphorus-based flame retardant may include red phosphorus, phosphoric acid ester-based, phosphate-based, phosphonate-based, phosphinate. (phosphinate-based), phosphine oxide-based and phosphazene-based flame retardants. In detail, for example, triphenyl-phosphate (TPP), resorcinol bis (diphenylphosphate), RDP, tetrakis bisphenol A diphosphate (bisphenol A) Bis(diphenylphosphate), BDP), hexaphenoxytricyclophosphazene, ammonium polyphosphate (APP), melamine phosphate (MP) and 9,10-dihydro-9-oxa -10-phosphaphene-10-oxide (9,10-dihydrro-9-oxa-10-phosphophenanthrene-10-oxide, DOPO).

Examples of the inorganic flame retardant may include a boron compound, an antimony trioxide, an aluminum hydroxide, a magnesium hydroxide, and the like.

However, the invention is not limited to the type of flame retardant.

The above flame retardant is contained in an amount of from 1 to 20% by weight, preferably from about 10 to about 18% by weight, based on the total mass of the resin composition. When the content of the flame retardant contained is less than a specific range, the resulting resin composition and formed body cannot exhibit sufficient flame retarding effect. When the content of the flame retardant contained exceeds a specific range, the resulting resin composition and the flame retardant in the formed body may be eluted, and physical properties (such as impact strength, elastic strength, and transparency) may be used. ) will drop significantly, especially causing a problem of a significant decrease in heat resistance.

According to another embodiment of the present invention, the polymer resin composition may further comprise one or more copolymers selected from the group consisting of aromatic vinyl-unsaturated nitrile copolymers, unsaturated nitrile-diene Base rubber-aromatic vinyl graft copolymer, alkyl methacrylate-diene -based rubber-aromatic vinyl graft copolymer) and a group consisting of alkyl methacrylate-silicon-alkyl acrylate graft copolymer.

In this case, it is selected from the group consisting of an aromatic vinyl-unsaturated nitrile copolymer, an unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-diene rubber-aromatic vinyl The content of the one or more copolymers of the group consisting of the base graft copolymer and the monoalkyl methacrylate-ruthenium-alkyl acrylate graft copolymer is from about 1 to about the total weight of the resin composition. 25 wt%, and preferably from about 5 to about 20 wt%.

When the content of the above copolymer is less than a specific range, there is a problem that the impact resistance is lowered. When the content of the copolymer is higher than a specific range, there is no effect on lifting mechanical and physical properties such as strength and heat resistance, or there may be a problem that flame retardancy and chemical resistance are lowered.

In this case, the diene-based rubber may be a butadiene type rubber or an isoprene-type rubber. The unsaturated nitrile may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and alpha-chloroacrylonitrile. a group consisting of (α-chloroacrylonitrile). The aromatic vinyl may be one or more selected from the group consisting of styrene, α-methyl styrene vinyl toluene, t-butyl styrene, Halogen-substituted styrene, 1,3-dimethyl styrene, 2,4-dimethyl styrene and B A group consisting of ethyl styrene.

Further, the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer is preferably an acrylonitrile-butadiene-styrene graft copolymer and an alkyl methacrylate. The ester-diene rubber-aromatic vinyl graft copolymer is preferably a methyl methacrylate-butadiene-styrene graft copolymer. Further, the alkyl methacrylate-oxime-alkyl acrylate graft copolymer is preferably a methyl methacrylate-silicon-butyl acrylate graft copolymer.

Further, the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer is a core-shell rubber produced by an emulsion polymerization or a bulk polymerization method, which has An average particle diameter of from about 0.01 to about 5 microns and a graft rate of from about 5 to about 90%, and the core has a glass transition temperature of less than or equal to about -20 ° C, and the outer shell has a greater than Or equal to a glass transition temperature of about 20 °C. The outer shell may optionally include or not include a functional group such as glycidyl methacrylate or maleic anhydride.

On the other hand, the core-shell type rubber may selectively have a monomodal distribution form, and the average particle diameter ranges from about 0.01 to about 5 μm, or a multimodal distribution form, and The average particle size ranges from about 0.01 to about 5 microns.

Further, the polymer resin composition may further comprise one or more selected from the group consisting of unsaturated nitrile-aromatic vinyl-glycidyl methacrylate-based compatibilizer, unsaturated Unsaturated nitrile-aromatic vinyl-maleic anhydride-based compatibilizer, saturated ethylene-alkyl acrylate-glycidyl methacrylate-based compatibilizer (saturated ethylene- A group consisting of an alkyl acrylate-glycidyl methacrylate-based compatibilizer and a carbodiimide-based anti-hydrolysis agent.

In this case, the unsaturated nitrile-aromatic ethylene-glycidyl methacrylate-based compatibilizer may be included in an amount of less than or equal to 15% by weight, including the unsaturated nitrile-aromatic ethylene-cis. The butenedi anhydride-based compatibilizer may have a content of less than or equal to 15% by weight, and the saturated ethylene-alkyl acrylate-glycidyl methacrylate-based compatibilizer may comprise less than or equal to 15% by weight. The content, and the diimidrenide carbon-based anti-hydrolysis agent included may have a content of less than or equal to 10% by weight.

The alkyl acrylate may be one or more selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate. ), a group consisting of hexyl acrylate, octyl acrylate, and 2-ethyl hexyl acrylate.

Further, the unsaturated nitrile-aromatic ethylene-glycidyl methacrylate-based compatibilizer may have a glass transition temperature of from about 20 to about 200 ° C and a weight average molecular weight of from about 200 to about 300,000, and which may optionally be Aromatic ethylene-glycidyl methacrylate replacement.

The unsaturated nitrile-aromatic ethylene-maleic anhydride based compatibilizer can have a glass transition temperature of from about 20 to about 200 ° C and a weight average molecular weight of from about 200 to about 300,000. The saturated ethylene-alkyl acrylate-glycidyl methacrylate-based compatibilizer can have a glass transition temperature of from about -150 to about 200 ° C and a weight average molecular weight of from about 200 to about 300,000.

Further, the diindeninated carbon-based antihydrolysis agent may have a weight average molecular weight of from about 50 to about 300,000, and it may be as shown in the following Chemical Formula 4 or Chemical Formula 5:

Chemical formula 4

In Chemical Formula 4, C is carbon, N is nitrogen, and R _a and R _b are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or having 6 to 36 carbon atoms. An aryl group.

Chemical formula 5

In Chemical Formula 5, C is carbon, N is nitrogen, R _c is an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 36 carbon atoms, and n is an integer of 2 to 30,000, which means polymerization The average degree.

Further, according to an embodiment of the present invention, the polymer resin composition may further comprise one or more additives selected from the group consisting of dyes, pigments, impact modifiers, fillers. , stabilizers, lubricants, antioxidants, antimicrobial agents, releasing agents, anti-hydrolysis agents, plasticizers, nucleating agents, organic - a group consisting of an organic-inorganic particle or a mixture of the above.

Further, for example, a phenol-based primary antioxidant, a phosphite-based secondary antioxidant, a thioester-based antioxidant, or the like can be used as the above antioxidant. . In this case, the aromatic primary antioxidant may have a weight average molecular weight of from 50 to 300,000. The phosphite-based secondary antioxidant may, for example, be selected from the group consisting of Chemical Formula 6 to Chemical Formula 8 below, and the thioester-based antioxidant may be a compound represented by Chemical Formula 9 or Chemical Formula 10:

Chemical formula 6

In Chemical Formula 6, O is oxygen, P is phosphorous, and R _d and R _e are each independently an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms or 6 to 40. An unsubstituted or substituted aromatic group of one carbon atom.

Chemical formula 7

In Chemical Formula 7, O is oxygen, P is phosphorus, and R _f and R _g are each independently an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms or an unsubstituted 6 to 40 carbon atom. A substituted or substituted aromatic group, and n is an integer greater than 1, which represents a substituted repeating unit.

Chemical formula 8

In Chemical Formula 8, O is oxygen, P is phosphorus, and R _h , R _i , R _j and R _k are each independently an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms or having 6 to 40 An unsubstituted or substituted aromatic group of one carbon atom.

Chemical formula 9

Chemical formula 10

In Chemical Formula 9 and Chemical Formula 10, C is carbon, O is oxygen, S is sulfur, and R _m and R _n are each independently an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms or An unsubstituted or substituted aromatic group having 6 to 40 carbon atoms.

The above lubricant may be one or more selected from the group consisting of metal stearate-based lubricants, amide-based lubricants, and paraffin-based lubricants. Grouped with ester-based lubricants.

The above stabilizer may be a hindered amine light stabilizer (HALS), a benzotriazole-based light absorber or a benzophenone-based light absorber (benzophenone-based light absorber). ).

The pigment may include an inorganic pigment or an organic pigment or the like. The inorganic salt material includes carbon black, titanium oxide, zinc oxide or iron oxide. Organic pigments include cyanine-based pigments, phosphorous-based pigments, quinone-based pigments, perinone-based pigments, isoporphyrins Isoindolinone-based pigment or thioindigo-based pigment.

The above plasticizer may include, for example, diethyl phthalate, dioctyl phthalate or dicyclohexyl phthalate phthalate. Phthalic acid ester-based plasticizer, such as di-1-butyl adipate, adipic acid, di-n-octyl adipate Adipate), sebacic acid, di-n-butyl phthalate, azelaic acid or di(2-ethylhexyl) (di-2-ethyl) Hexyl) analiphatic dibasic acid ester-based plasticizer, such as diphenyl 2-ethylhexyl phosphate, diphenyloctyl phosphate (diphenyloctyl phosphate) Diphenyl octyl phosphate) phosphate ester-based plasticizer, such as acetyl tributyl citrate, acetyl triethyl citrate (acetyl tri) -2-ethylhexyl citrate), polyhydric hydroxy carboxylic acid ester of tributyl citrate For example, methyl acetyl ricinoleate, a fatty acid ester-based plasticizer of amyl stearate, such as glycerin triacetate Polyhydric alcohol ester-based plasticizers, such as epoxidized butyl esters of fatty acids or epoxidized octyl stearate An epoxy-based plasticizer.

The above organic-inorganic microparticles may include silica, colloidal silica, alumina, alumina sol, talc, titanium dioxide, mica. (mica), calcium carbonate, polystyrene, polymethylmethacrylate, silicon, and the like. Particles are not limited to being surface treated, but when surface treated titanium dioxide or talc is used, their overall physical properties (such as stiffness and impact strength) are well balanced and exhibit specific gravity (specific Gravity) The effect of lowering and improving heat resistance and injection moldability. The surface treatment may be carried out, in particular, by chemical or physical methods and using a treating agent such as a silane coupling agent, a higher fatty acid, a metal salts of fatty acids, Unsaturated fatty acid, organic titanate, resin acid or polyethylene glycol. The inorganic fine particles may have an average particle size of from about 1 to about 30 μm, preferably from about 1 to about 15 μm, and have an effect of improving heat resistance and rigidity within the above range.

The nucleating agent may include a sorbitol-based metal salt, a phosphate-based metal salt, a quinacridone, a calcium carboxylate, a guanamine group. An amide-based organic compound or the like, and a phosphate-based metal salt is preferably used.

According to another embodiment of the present invention, the above polymer resin composition may have a tensile strength loss defined by the following formula 1 in the range of from about 0.5 to about 20%, and Formula 1 is:

Tensile strength loss (%) = [(tensile strength before test - tensile strength after test) / tensile strength before test] x 100.

The tensile strength before the test and the tensile strength after the test were measured by the following methods. The polymer resin composition is pelletized by uniformly kneading and extrude. The produced particles were injected in the same manner at a temperature of about 250 °C. The sample injected for testing the tensile strength was adjusted for 24 hours at a temperature of about 23 ± 2 ° C and a relative humidity of about 50 ± 5%. A chemical resistance test fixture having a deformation amount of about 2.2% was prepared, and the sample was fixed to the test fixture. Next, the test sample was supplied to a blend of an aromatic/aliphatic chemical or UV light blocker for about 1 minute and then allowed to stand at about 23 ± 2 ° C for 72 hours. Thereafter, the tensile strength of the test sample before and after the test is measured. However, the blend of aromatic/aliphatic chemical agents comprises from about 10 to 90% by weight of ethanol, and may additionally comprise one or more selected from the group consisting of aliphatic and aromatic alcohols, aliphatic and Aromatic and aromatic esters, aromatic aldehydes, unsaturated hydrocarbons, saturated hydrocarbons, aliphatic amines, aliphatic diamines An accessory component of a group of intellectual diamines and terpene.

Further, when a 3.0 mm polymer resin composition is supplied to the UL94 V test (vertical burning test), the polymer resin composition may have flame retardancy higher than or equal to V-0.

In the following, the operation and efficacy of the present invention will be described in more detail by way of specific examples. However, the following examples are only for understanding the present invention, and the scope of the present invention is not limited thereto.

Example

A conventional polycarbonate (PC) resin, styrene-acrylonitrile (SAN) resin, and acrylonitrile-butadiene containing about 60% by weight of butadiene rubber are prepared. Acrylonitrile-butadiene-styrene (ABS) resin powder, resorcinol bis(diphenyl phosphate) flame retardant and tetraphenyl bisphenol A diphosphate flame retardant.

Preparation of polyester resin

Preparation Example A:

Terephthalic acid (6 moles) was used as the dicarboxylic acid component, 1,4-cyclohexanedimethanol (138 g, 0.957 mol), ethylene glycol (313 g, 5.043 mol) and isosorbide ( 105 g, 0.718 mol) was placed as a glycol component in a 3 liter reactor equipped with a stirrer and a discharge condenser to prepare the reaction. The reaction mixture was supplied at a temperature of 255 ° C to carry out an esterification reaction. In this case, the generated water is discharged to the outside. After the completion of the production and drainage, the produced esterified product is transferred to a polycondensation reactor equipped with a stirrer, a condenser and a vacuum system.

A catalyst, a stabilizer, and a colorant are added to the mixture. After the internal temperature of the reactor was raised to 265 ° C, ethylene glycol was removed under a reduced pressure of 500 mmHg for 40 minutes. Next, the pressure was reduced to 0.1 mmHg and a polycondensation reaction was carried out to prepare a polyester resin. The polyester resin thus prepared had a weight average molecular weight (Mw) of 63,000 (g/mol) and an intrinsic viscosity of 0.76 (dl/g).

Preparation Example B:

A polyester resin was prepared in the same manner as in Preparation Example A except that terephthalic acid (6 mol) was used as the dicarboxylic acid component, 1,4-cyclohexanedimethanol (565 g, 3.918 mol) Ethylene glycol (96 g, 1.547 mol) and isosorbide (789 g, 5.399 mol) were used as the glycol component. The polyester resin thus prepared had a weight average molecular weight (Mw) of 37,000 (g/mol) and an intrinsic viscosity of 0.65 (dl/g).

Preparation of polyester resin composition

According to the ratio of each component shown in Table 1 and Table 2 below, a double-screw kneading extruder (Φ: 40 mm, at a cylinder temperature of 250 ° C and a die temperature of 245 ° C) was used. L/D = 44) The components were uniformly kneaded and extruded to prepare a polymer resin composition having a particulate form.

Table 1

Table 2

Experimental example

Tensile property test

Using the polymer resin composition prepared as in the above Examples and Preparation Examples, a dog bone-shaped sample having a size of 150 mm × 12.7 mm × 3.2 mm was prepared in accordance with the ASTM D638 standard, and a Universal Test Machine was used. To measure the tensile properties.

In Tables 3 and 4, the terms regarding the tensile properties are as follows:

Tensile strength (@Y): tensile strength at the point of relief;

Tensile property extension (@Y): tensile elongation at the point of relief;

Tensile strength (@B): tensile strength at breakpoints;

Tensile property extension (@B): Tensile elongation at breakpoints.

Chemical resistance test

Using a polymer resin composition prepared as in the above examples and preparation examples, a dog bone-shaped sample having a size of 150 mm × 12.7 mm × 3.2 mm was prepared in accordance with ASTM D638 standard, and then at a temperature of about 23 ± 2 ° C and It was allowed to adjust for 24 hours at a relative humidity of about 50 ± 5%. The calculation is performed by the following method.

(1) A chemical resistance test fixture having a deformation amount of about 2.2% was prepared, and the sample was fixed to the test fixture.

(2) The test sample was supplied to a blend of an aromatic/aliphatic chemical or UV light blocker for about 1 minute, and then allowed to stand at about 23 ± 2 ° C for 72 hours.

(3) After 72 hours at 23±2 ° C, the tensile strength before and after the test is measured and the tensile strength loss (%) is calculated by the following formula 1, and the above chemical resistance can be compared and sought Out. Equation 1 is:

Tensile strength loss (%) = [(tensile strength before test - tensile strength after test) / tensile strength before test] x 100.

The above blend of aromatic/aliphatic chemical agents includes from about 10 to 90% by weight of ethanol and additionally includes one or more selected from the group consisting of the following accessory ingredients.

The accessory components include aliphatic and aromatic alcohols, aliphatic and aromatic esters, aromatic aldehydes, unsaturated hydrocarbons, saturated hydrocarbons, aliphatic amines, aliphatic diamines, and terpenes.

Further, as for the UV light blocker, a product in the field of common UV light blockers can be selected.

In Tables 3 and 4 below, the terms for tensile strength loss are as follows:

Tensile strength loss (A): Loss of tensile strength when supplied to a blend of alcohol-based aromatic/aliphatic chemical agents.

Tensile strength loss (B): Loss of tensile strength when supplied to a UV light blocker.

Flexural property test

Using the polymer resin composition prepared as in the above Examples and Preparation Examples, a dog bone-shaped sample having a size of 127 mm × 12.7 mm × 6.4 mm was prepared in accordance with the ASTM D740 standard and the flexural characteristics were measured using a universal testing machine. .

Impact characteristic experiment

Using the polymer resin compositions prepared as in the above examples and preparation examples, test samples having a size of 64.0 mm × 12.7 mm × 3.2 mm (3.2 T sample, 3.2 T, RT) and having 64.0 mm × 12.7 mm, respectively, were prepared. Test specimens of 6.4 mm size (6.4 T sample, 6.4 T, RT) were tested for impact characteristics at 23 ° C using an Izode impact tester in accordance with ASTM D256.

Heat resistance test

Using a polymer resin composition prepared as in the above Examples and Preparation Examples, a sample having a size of 127 mm × 13 mm × 10 mm was prepared, and the thermal deformation was measured in accordance with ASTM D648 when it was supplied under a pressure of 0.455 MPa. Heat distortion temperature/heat deflection temperature (HDT).

Flame retardant test

The polymer resin composition prepared as in the above Examples and Preparation Examples was used, and the sample size was 127 mm × 12.7 mm × 3.0 mm, and then the flame retardancy was measured in accordance with the UL94 V test (vertical burning test).

The results of the above experiments are summarized in Tables 3 and 4 below.

table 3

Table 4

Referring to Tables 3 and 4 above, it can be confirmed that the embodiment of the present invention exhibits not only excellent mechanical properties (for example, tensile properties, flexural properties, impact properties, and heat resistance) but also significant improvement over the comparative examples. Chemical resistance and flame retardancy.

In particular, compared with the comparative examples, it was confirmed that the flame retardancy measured in the examples of the present invention is a V-0 grade which is excellent in flame retardancy, and an anti-resistant property as an index of chemical resistance. The tensile strength loss was about 3-13%, which was also greatly improved compared to the comparative example.

Further, it can be seen that Comparative Example 7 exhibits some results similar to those of the embodiment of the present invention, such as flame retardancy, chemical resistance, and the like. However, Comparative Example 7 contained a small amount of polycarbonate resin, and therefore the tensile properties and flexural properties of Comparative Example 7 were inferior compared to the examples of the present invention. In particular, it was confirmed that in the example of Comparative Example 7, the measured heat distortion temperature was 60 ° C or less, and thus the heat resistance was largely lowered. The above are only the preferred embodiments of the present invention, and all changes and modifications made to the scope of the present invention should be within the scope of the present invention.

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Claims (17)

A polymer resin composition comprises: 5 to 70% by weight of a polyester resin, a residue comprising a dicarboxylic acid component and a glycol a residue of a diol component, wherein the residue of the dicarboxylic acid component comprises terephthalic acid, and the residue of the diol component comprises 5 to 60 mole percent (mol%) of yam pear Alcohol (isosorbide), cyclohexanedimethanol in an amount of 5 to 80 mol%, and other diol compound in a remaining amount; 15 to 65 wt% of a polycarbonate resin; and 1 to 20 One percent by weight of a flame retardant. The polymer resin composition according to claim 1, wherein the polyester resin has a weight average molecular weight of 10,000 to 100,000 g/mol and a glass transition temperature of 0 to 200 °C. . The polymer resin composition according to claim 1, wherein the polycarbonate resin has an average molecular weight of one weight from 10,000 to 100,000 g/mol and a glass transition temperature of from 50 to 200 °C. The polymer resin composition according to claim 1, wherein the dicarboxylic acid component in the polyester resin comprises one or more aromatic dicarboxylic acids selected from the group consisting of 8 to 20 carbon atoms. And a group consisting of aliphatic dicarboxylic acids having 4 to 20 carbon atoms. The polymer resin composition according to claim 1, wherein the glycol component in the polyester resin comprises one or more groups selected from the group consisting of compounds represented by the following Chemical Formula 1, Chemical Formula 2 and Chemical Formula 3 : In Chemical Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms. n ₁ and n ₂ are each independently an integer of 0 to 3; In Chemical Formula 2, each of R ₅ , R ₆ , R ₇ and R _{8 is} each independently hydrogen or an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms; In Chemical Formula 3, n ₃ is an integer of 1 to 7. The polymer resin composition of claim 1, wherein the flame retardant comprises one or more selected from the group consisting of a halogen-based flame retardant, a phosphorus-based flame retardant And a group consisting of inorganic flame retardants. The polymer resin composition according to claim 1, further comprising one or more copolymers selected from the group consisting of aromatic vinyl-unsaturated nitrile copolymers and unsaturated nitriles. Unsaturated nitrile-diene-based rubber-aromatic vinyl graft copolymer, alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer -diene-based rubber-aromatic vinyl graft copolymer) and a group consisting of alkyl methacrylate-silicon-alkyl acrylate graft copolymer. The polymer resin composition according to claim 7, which is selected from the group consisting of an aromatic vinyl-unsaturated nitrile copolymer, an unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, and an alkyl methacrylate. The content of the or the copolymer of the diene-based rubber-aromatic vinyl graft copolymer and the monoalkyl methacrylate-oxime-alkyl acrylate graft copolymer is from 1 to 25 by weight. %. The polymer resin composition according to claim 7, wherein the diene-based rubber is a butadiene type rubber or an isoprene-type rubber. The polymer resin composition according to claim 7, wherein the unsaturated nitrile is one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. a group consisting of phenylacrylonitrile and α-chloroacrylonitrile. The polymer resin composition according to claim 7, wherein the aromatic vinyl is one or more selected from the group consisting of styrene, α-methyl styrene vinyl toluene ), t-butyl styrene, halogen-substituted styrene, 1,3-dimethyl styrene, 2,4-di A group consisting of 2,4-dimethyl styrene and ethyl styrene. The polymer resin composition according to claim 7, wherein the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer is an acrylonitrile-butadiene graft copolymer (acrylonitrile-butadiene). -styrene graft copolymer). The polymer resin composition according to claim 7, wherein the alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer is a methyl methacrylate-butadiene-styrene graft copolymerization. Methyl methacrylate-butadiene-styrene graft copolymer. The polymer resin composition according to claim 7, wherein the alkyl methacrylate-oxime-alkyl acrylate graft copolymer is methyl methacrylate-methyl methacrylate-glycol copolymer (methyl methacrylate- Silicon-butyl acrylate graft copolymer). The polymer resin composition according to claim 1, wherein the polymer resin composition has a tensile strength loss defined by the following formula 1 in the range of 0.5 to 20%, and the formula 1 is: Tensile strength loss (%) = [(tensile strength before test - tensile strength after test) / tensile strength before test] x 100. The polymer resin composition according to claim 1, wherein when the polymer resin composition of 3.0 mm is supplied to the UL94 V test (vertical burning test), the polymer resin composition has a higher than or equal to V- One of the 0 grades is flame retardancy. The polymer resin composition according to claim 1, further comprising one or more additives selected from the group consisting of dyes, pigments, impact modifiers, and fillers. , stabilizer, lubricant, antioxidant, antimicrobial agent, releasing agent, anti-hydrolysis agent, plasticizer, A group consisting of a nucleating agent, an organic-inorganic particle, or a mixture of the above.