KR20160075207A - Polymer resin composition having excellent flame retardancy - Google Patents

Abstract

The present invention relates to a polymeric resin composition. More specifically, the present invention relates to a polymeric resin composition which exhibits improved material properties including heat resistance and impact resistance as well as outstanding chemical resistance and flame retardancy. To this end, the polymeric resin composition contains 5-70 wt% of a polyester resin, 15-65 wt% of a polycarbonate resin, and 1-20 wt% of a flame retardant.

Description

[0001] POLYMER RESIN COMPOSITION HAVING EXCELLENT FLAME RETARDANCY [0002]

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

Since polyester resins have relatively excellent heat resistance, mechanical strength and elastic strength, they are widely used as reinforcing plastics, paints, films, molding resins, etc., and are also used as textile materials for garments. Due to their characteristic properties, Construction interior materials, molded signboards, and the like.

However, since polyester resins have lower heat resistance than other polymer materials such as acrylic materials or polycarbonate-based materials and deteriorate or deform due to changes in the surrounding environment, polyester resins can not be used alone for outdoor exterior materials or automobile parts There was a problem unsuitable for the following.

On the other hand, polycarbonate resin is a synthetic resin having impact resistance or heat resistance and is used in various fields such as appearance of various building materials and electronic products, packaging materials, cases, boxes, interior and exterior materials. Such polycarbonate resins are in great demand due to their excellent mechanical properties. However, appearance colors of polycarbonate are changed or cracks are generated by various detergents, cosmetics for women and hand disinfectants for infants, which are commonly used in the market, There is a problem that the product is deteriorated.

Various attempts have been made to solve the problems of the above-mentioned polyester resin or polycarbonate resin, and research on a method of blending a polyester resin and a polycarbonate resin has been continued.

In particular, in order to be used in electric, electronic products and office equipment where heat is generated during use such as a monitor or a facsimile, or in a material susceptible to an environment such as a fire or the like, the resin composition must have flame retardancy. The carbonate resin is easily burned. In addition, since the polyester resin and the polycarbonate resin have different melt viscosities and molecular structures, there is a certain limit in improving the flame retardancy by simply blending them.

Accordingly, a flame retardant is used in order to impart flame retardancy to the resin composition. When a flame retardant is used in a high content in order to obtain a high flame retardancy, elution of the flame retardant may occur and impact strength, And the like. In particular, there is a disadvantage that the heat resistance is significantly lowered.

In addition, various methods have been used to increase the chemical resistance while maintaining the mechanical properties of polycarbonate, in particular, heat resistance. However, the degree of improvement in chemical resistance is not sufficient enough to be applicable in actual industrial applications. There is a problem that the characteristics are deteriorated. Further, in order to simultaneously improve the heat resistance and the chemical resistance, a method of further blending one or more materials has been tried, but it has been difficult to exhibit an appropriate level of chemical resistance.

Therefore, there is still a need for studies on a polymer resin excellent in chemical resistance and flame retardancy, while maintaining superior complementary physical properties such as strength, transparency and heat resistance in polyester resins and polycarbonate resins.

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

The present invention includes residues of a dicarboxylic acid component comprising terephthalic acid and residues of a diol component comprising 5 to 60 mol% of isosorbide, 5 to 80 mol% of cyclohexanedimethanol and remaining amounts of other diol compounds 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.

According to one embodiment of the invention, the polyester resin may have a weight average molecular weight of from about 10,000 to about 100,000 g / mol, a glass transition temperature of from about 0 to about 200 ° C, and the polycarbonate resin has a weight average molecular weight From about 10,000 to about 100,000 g / mol, and a glass transition temperature from about 50 to about 200 < 0 > C.

The dicarboxylic acid component of the polyester resin may include at least one 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 , And the diol component in the polyester resin may include at least one member selected from the group consisting of compounds represented by the following formulas (1), (2) and (3).

[Chemical Formula 1]

R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms; n ₁ and n ₂ are each independently an integer of 0 to 3; ego,

(2)

In Formula 2, R ₅ , R ₆ , R _7, and R ₈ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,

 (3)

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

The flame retardant may include at least one selected from the group consisting of a halogen flame retardant, a phosphorus flame retardant, and an inorganic flame retardant.

According to another embodiment of the present invention, the polymeric resin composition may include an aromatic vinyl-unsaturated nitrile copolymer, an unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-diene rubber-aromatic vinyl graft Copolymers, and alkyl methacrylate-silicone-alkyl acrylate graft copolymers.

Here, the aromatic vinyl-unsaturated nitrile copolymer, the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, the alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, and the alkyl methacrylate- The content of the at least one copolymer selected from the group consisting of the graft copolymer may be about 1 to about 25% by weight.

The diene rubber may be a butadiene rubber or an isoprene rubber, and the unsaturated nitrile may be an acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, and? -Chloroacrylonitrile And the aromatic vinyl may be at least one selected from the group consisting of styrene,? -Methylstyrene vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, And may be at least one selected from the group consisting of

According to one example, the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer, and the alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer May be a methyl methacrylate-butadiene-styrene graft copolymer, and the alkyl methacrylate-silicone-alkyl acrylate graft copolymer is preferably a methyl methacrylate-silicone-butyl acrylate graft copolymer can do.

According to another embodiment of the present invention, the polymer resin composition may have a tensile strength loss rate represented by the following general formula (1): about 0.5 to about 20%.

[Formula 1]

Tensile strength loss rate (%) = [(Tensile strength before test - Tensile strength after test) / Tensile strength before test] × 100

The polymeric resin composition may have flame retardancy of V-0 or higher at about 3.0 mm under UL 94 V Test (Vertical Burning Test).

The polymeric resin composition may further comprise one or more kinds selected from the group consisting of a dye, a pigment, an impact modifier, a filler, a stabilizer, a lubricant, an antioxidant, an antibacterial agent, a releasing agent, Or more of the above additives.

The polymer resin composition of the present invention exhibits mechanical properties such as excellent strength, transparency and heat resistance, and has excellent flame retardancy.

The polymer resin composition of the present invention comprises a residue of a dicarboxylic acid component containing terephthalic acid and a diol component containing 5 to 60 mol% of isosorbide, 5 to 80 mol% of cyclohexanedimethanol and remaining amounts of other diol compounds From 5 to 70% by weight of a polyester resin comprising residues of 15 to 65% by weight of a polycarbonate resin; And 1 to 20% by weight of a flame retardant.

Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, integers, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the present invention will be described in more detail.

According to one embodiment of the present invention there is provided a process for the preparation of a diol compound comprising the reaction of a residue of a dicarboxylic acid component comprising terephthalic acid with 5 to 60 mol% of isosorbide, 5 to 80 mol% of cyclohexanedimethanol, From 5 to 70% by weight of a polyester resin comprising a residue of a diol component; 15 to 65% by weight of a polycarbonate resin; And 1 to 20% by weight of a flame retardant.

Although there has been proposed a method of mixing specific polymer resins to complement or enhance the physical properties of the polyester resin before, there has been a certain limit to the improvement effect or complementary synergistic effect by mixing these components, and sufficient mechanical properties And it was not easy to secure flame retardancy.

Accordingly, the inventors of the present invention have continued to carry out research on a polymer resin composition that exhibits excellent mechanical properties and flame retardancy and is applicable to various electrical and electronic equipment, office equipment, automobile parts, household goods, and construction members, It has been confirmed through experiments that the resin, the polycarbonate resin, and the flame retardant are mixed in a specific amount to obtain a polymer resin composition exhibiting excellent flame retardancy together with physical properties such as excellent impact resistance and heat resistance.

The polymeric resin composition may be prepared by using any conventional method and apparatus used for producing a blend or mixture of polymeric resins without any particular limitation. For example, polycarbonate resins; Polyester resin; And a flame retardant; in a conventional mixer, a blender or a tumbler, and mixing the mixture through a twin-screw kneading extruder, the polymer resin composition may be provided. In the course of producing the polymer resin composition, it is preferable that each of the resins is used in a sufficiently dried state.

On the other hand, in the polymer resin composition of one embodiment, the polyester resin may contain 5 to 60 mol% of isosorbide, 5 to 80 mol% of cyclohexanedimethanol, and 5 to 80 mol% of cyclohexanedimethanol in the remaining portion of the dicarboxylic acid component containing terephthalic acid. And a diol component comprising a diol compound.

As used herein, the term " residue " refers to a certain moiety or unit derived from the specific compound that is included in the result of the chemical reaction when the particular compound participates in the chemical reaction. For example, each of the 'residue' of the dicarboxylic acid component or the 'residue' of the diol component may be derived from a moiety derived from a dicarboxylic acid component or from a diol component in a polyester formed by an esterification reaction or a polycondensation reaction It means the part derived.

The 'dicarboxylic acid component' may be a dicarboxylic acid such as terephthalic acid, an alkyl ester thereof (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) and / Is used to mean an acid anhydride and can react with a diol component to form a dicarboxylic acid moiety such as a terephthaloyl moiety.

As the dicarboxylic acid component used in the synthesis of the polyester includes terephthalic acid, physical properties such as heat resistance, chemical resistance, or flame retardancy of the polyester resin to be produced can be improved.

In addition, in the polyester resin, the dicarboxylic acid component may further include at least one selected from the group consisting of aromatic dicarboxylic acids having 8 to 20 carbon atoms and aliphatic dicarboxylic acids having 4 to 20 carbon atoms in addition to terephthalic acid can do.

The aromatic dicarboxylic acid component may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms, preferably 8 to 14 carbon atoms, or a mixture thereof. Examples of the aromatic dicarboxylic acid include naphthalenedicarboxylic acid such as isophthalic acid and 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 2, 5-furandicarboxylic acid, 2,5-thiopendicarboxylic acid, and the like, but the specific examples of the aromatic dicarboxylic acid are not limited thereto.

The aliphatic dicarboxylic acid component may be an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms, or a mixture thereof. Examples of the aliphatic dicarboxylic acid include cyclohexanedicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid, phthalic acid, sebacic acid, succinic acid, isodecylsuccinic acid, Linear or branched alicyclic dicarboxylic acid components such as maleic acid, fumaric acid, adipic acid, glutaric acid and azelaic acid. However, the specific examples of the aliphatic dicarboxylic acid are not limited thereto.

On the other hand, the dicarboxylic acid component comprises about 50 to about 100 mole%, preferably about 70 to about 100 mole% terephthalic acid; And from about 0 to about 50 mol%, preferably from about 0 to about 30 mol%, of at least one dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acids and aliphatic dicarboxylic acids. If the content of terephthalic acid in the above dicarboxylic acid component is too small or too large, physical properties such as heat resistance, chemical resistance or weather resistance of the polyester resin may be deteriorated.

On the other hand, the diol component used in the synthesis of the polyester may include 5 to 60 mol% of isosorbide, 5 to 80 mol% of cyclohexanedimethanol, and the remaining amount of other diol compounds.

As the diol component includes isosorbide (1,4: 3,6-dianhydroglucitol), the heat resistance of the produced polyester resin is improved, and physical properties such as chemical resistance and chemical resistance can be improved . The content of cyclohexane dimethanol (for example, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol or 1,4-cyclohexane dimethanol) in the diol component is increased The higher the impact strength of the polyester resin to be produced.

As the diol component includes isosorbide (1,4: 3,6-dianhydroglucitol), the heat resistance of the produced polyester resin is improved, and physical properties such as chemical resistance and chemical resistance can be improved . The content of cyclohexane dimethanol (for example, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol or 1,4-cyclohexane dimethanol) in the diol component is increased The higher the impact strength of the polyester resin to be produced.

The diol component may further include other diol components in addition to the isosorbide and cyclohexane dimethanol. The 'other diol component' means a diol component other than the isosorbide and cyclohexane dimethane, and may be, for example, an aliphatic diol, an aromatic diol, or a mixture thereof.

The diol component in the polyester resin may include at least one member selected from the group consisting of compounds represented by the following formulas (1), (2) and (3).

[Chemical Formula 1]

R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms; n ₁ and n ₂ are each independently an integer of 0 to 3; ego,

(2)

In Formula 2, R ₅ , R ₆ , R _7, and R ₈ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,

 (3)

In 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.

Such a polyester resin is contained in an amount of 5 to 70 wt%, preferably about 10 to about 70 wt%, more preferably about 20 to about 60 wt%, based on the total weight of the resin composition. When the content of the polyester resin is not more than a specific value, there is a problem that the chemical resistance is lowered and the loss ratio of the tensile strength is increased, and when the content of the polyester resin is more than the specific amount, the heat resistance is lowered.

On the other hand, the polyester resin is obtained by esterifying a dicarboxylic acid component containing terephthalic acid with a diol component containing 5 to 60 mol% of isosorbide, 5 to 80 mol% of cyclohexanedimethanol and other remaining diol compounds ; Adding a phosphorus stabilizer when the esterification reaction proceeds at least 80%; And a step of subjecting the esterification reaction product to a polycondensation reaction.

According to such a method for producing a polyester resin, an esterification reaction catalyst containing a zinc-based compound is used, and a phosphorus stabilizer is added to the reaction solution at the end of the esterification reaction, for example, And polycondensation of the resultant product of the esterification reaction can provide a polyester resin which exhibits properties such as high heat resistance, flame retardancy and impact resistance, and has excellent appearance characteristics, high transparency and excellent molding properties.

Specific details of the dicarboxylic acid component containing terephthalic acid, cyclohexanedimethanol, isosorbide and other diol compounds are as described above.

Specific examples of the zinc-based catalysts include zinc acetate, zinc acetate dihydrate, and mixtures thereof. Specific examples of the phosphorus stabilizer include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonoacetate, And mixtures of two or more.

The esterification reaction step may be carried out by reacting the dicarboxylic acid component and the diol 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 esterification reaction conditions can be appropriately controlled according to the specific properties of the polyester to be produced, the mole ratio of the dicarboxylic acid component to the glycol, or the process conditions. Specifically, preferred examples of the esterification reaction conditions include a pressure of about 0 to about 5.0 kg / cm 2, more preferably about 0.1 to about 3.0 kg / cm 2; A temperature of from about 200 to about 270 캜, more preferably from about 240 to about 260 캜.

The esterification reaction may be carried out batchwise or continuously, and each raw material may be separately added. However, it is preferable to add the diol component in the form of a slurry in which a dicarboxylic acid component is mixed . The diol component, which is a solid component at room temperature, may be dissolved in water or ethylene glycol and mixed with a dicarboxylic acid component such as terephthalic acid to form a slurry. Alternatively, after the isosorbide is melted at 60 DEG C or higher, a dicarboxylic acid component such as terephthalic acid and other diol components may be mixed to form a slurry. In addition, water may be further added to a slurry containing a copolymerized diol component such as a dicarboxylic acid component, isosorbide, and ethylene glycol to help increase the fluidity of the slurry.

The molar ratio of the dicarboxylic acid component and the diol component participating in the esterification reaction may be about 1: 1.05 to about 1: 3.0. If the molar ratio of the dicarboxylic acid component to the diol component is less than about 1.05, the unreacted dicarboxylic acid component may remain in the polymerization reaction and the transparency of the resin may be deteriorated. When the molar ratio exceeds about 3.0, The speed may be lowered or the productivity of the resin may be lowered.

The step of subjecting the esterification reaction product to a polycondensation reaction comprises reacting the esterification reaction product of the dicarboxylic acid component and the diol component at a temperature of about 150 to about 300 DEG C and a pressure of about 600 to about 0.01 mmHg Lt; RTI ID = 0.0 > 1 < / RTI > to about 24 hours.

Such a polycondensation reaction may be carried out at a reaction temperature of from about 150 to about 300 DEG C, preferably from about 200 to about 290 DEG C, more preferably from about 260 to about 280 DEG C; And a reduced pressure of from about 600 to about 0.01 mmHg, preferably from about 200 to about 0.05 mmHg, and more preferably from about 100 to about 0.1 mmHg. As the decompression condition of the polycondensation reaction is applied, the glycol, which is a by-product of the polycondensation reaction, can be removed from the system, so that when the polycondensation reaction is outside the range of about 400 to about 0.01 mmHg, can do.

In addition, when the polycondensation reaction occurs at a temperature outside the range of about 150 to about 300 ° C., the glycol, which is a by-product of the polycondensation reaction, can not be effectively removed from the system when the polycondensation reaction proceeds to about 150 ° C. or less, The physical properties of the polyester resin to be produced may be lowered. When the reaction proceeds at about 300 ° C or more, the appearance of the polyester resin to be produced is likely to become yellow. And, the polycondensation reaction can be carried out for a necessary time until the intrinsic viscosity of the final reaction product reaches an appropriate level, for example, for an average residence time of about 1 to about 24 hours.

On the other hand, the method for producing the polyester resin composition may further include a step of further adding a polycondensation catalyst. Such a polycondensation catalyst may be added to the product of the esterification reaction or the transesterification reaction before the start of the polycondensation reaction and added to the mixed slurry containing the diol component and the dicarboxylic acid component before the esterification reaction And may be added during the esterification reaction step.

As the polycondensation catalyst, a titanium compound, a germanium compound, an antimony compound, an aluminum compound, a tin compound, or a mixture thereof may be used.

Examples of the titanium compound include tetraethyl titanate, acetyl tripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, Titanium dioxide / zirconium dioxide copolymer, and the like can be given as examples of the titanium dioxide / zirconium oxide / titanium dioxide / titanate / titanium dioxide / titanium dioxide / titanium dioxide / titanium dioxide / titanium dioxide / titanate / acetylacetonate titanate, ethylacetoacetic ester titanate, isostearyl titanate, titanium dioxide, have.

Examples of the germanium compound include germanium dioxide (GeO ₂ ), germanium tetrachloride (GeCl ₄ ), germanium ethyleneglycoxide, germanium acetate, A mixture thereof, and the like. Preferably, germanium dioxide can be used, and both germanium dioxide can be crystalline or amorphous, and glycol solubility can also be used.

On the other hand, the polycarbonate resin can be blended with the polyester resin to improve mechanical properties such as impact strength, tensile strength and elongation of the resin composition, and also to significantly improve heat resistance.

As such a polycarbonate-based polymer, a polycarbonate-based polymer prepared using bisphenol-A as a basic constituent can be used in various ways. Specifically, a polycarbonate resin having various molecular weights and physical properties can be used without limitation, taking into account the characteristics of the resin molded product to be produced, for example, a weight average molecular weight of about 10,000 to about 100,000 g / mol, It is preferable to use a polycarbonate resin having a temperature of about 50 to about 200 캜.

The polycarbonate resin may be contained in an amount of 15 to 65 wt%, preferably about 20 to about 60 wt%, based on the total weight of the resin composition. If the content of the polycarbonate resin is less than the specific range, the effect of improving the mechanical properties such as strength, elongation, and heat resistance may be insignificant. If the content exceeds the specified weight, the chemical resistance, Can be degraded.

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

According to one example, the flame retardant may be a halogen flame retardant, a phosphorus flame retardant, an inorganic flame retardant, or a mixture thereof.

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

Phosphorous flame retardants include, for example, phosphorous, phosphoric acid ester, phosphate, phosphonate, phosphinate, phosphine oxide, and phosphazene flame retardants. Specific examples thereof include TPP (triphenyl phosphate), RDP (diphenylphosphate), bisphenol A bis (diphenylphosphate), hexaphenoxytricyclophosphazene, APP (ammonium polyphosphate), MP (melamine phosphate) and DOPO (9,10 dihydrro-9-oxa-10-phosphophenanthrene-10-oxide ) And the like.

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

However, the present invention is not necessarily limited to the types of the above-mentioned flame retardants.

The flame retardant may be contained in an amount of 1 to 20% by weight, preferably about 10 to 18% by weight based on the total weight of the resin composition. When the flame retardant is contained in an amount less than a predetermined amount, the flame retardant effect may not be sufficiently exhibited in the resin composition to be produced and the molded product, and when the flame retardant is contained in excess of the predetermined content, the flame retardant may be eluted from the resin composition, , The impact strength, the elastic strength, and the transparency are remarkably lowered, and in particular, the heat resistance is remarkably lowered.

According to another embodiment of the present invention, the polymeric resin composition may include an aromatic vinyl-unsaturated nitrile copolymer, an unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-diene rubber-aromatic vinyl graft Copolymers, and alkyl methacrylate-silicone-alkyl acrylate graft copolymers.

Here, the aromatic vinyl-unsaturated nitrile copolymer, the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, the alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, and the alkyl methacrylate-silicone- Acrylate graft copolymer may be contained in an amount of about 1 to about 25% by weight, and preferably about 5 to about 20% by weight, based on the total weight of the resin composition have.

When the above-mentioned copolymer is contained in an amount of less than a specific content, there may arise a problem that the impact resistance is lowered. When the content exceeds the specified content, there is no improvement in mechanical properties such as strength and heat resistance, There is a possibility that a problem of degradation may occur.

In this case, the diene rubber may be a butadiene rubber or an isoprene rubber, and the unsaturated nitrile may be composed of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, and? -Chloroacrylonitrile And the aromatic vinyl may be at least one selected from the group consisting of styrene,? -Methylstyrene vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, And may be at least one selected from the group consisting of

The unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer, and the alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer May be preferably methyl methacrylate-butadiene-styrene graft copolymer, and the alkyl methacrylate-silicone-alkyl acrylate graft copolymer is methyl methacrylate-silicone-butyl acrylate graft copolymer Lt; / RTI >

The above-mentioned unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer is a core-shell rubber prepared through a copolymerization polymerization or a bulk polymerization process, and has an average particle size of about 0.01 to about 5 μm and a graft rate of About 5 to about 90% of the core, a glass transition temperature of the core of about -20 占 폚 or less, a glass transition temperature of the shell of about 20 占 폚 or higher, and optionally, a shell of glycidyl methacrylate Or maleic acid anhydride, and the like.

On the other hand, the core-shell rubbers may optionally have a morphology in the form of a monomodal distribution having an average particle size of about 0.01 to about 5 탆, or a morphology having an average particle size of about 0.01 to about 5 탆 And may have a morphology in the form of a multimodal distribution.

In addition, the polymer resin composition may be used in combination with an unsaturated nitrile-aromatic vinyl-glycidyl methacrylate-based compatibilizer, an unsaturated nitrile-aromatic vinyl-maleic anhydride-based compatibilizer, a saturated ethylene-alkyl acrylate-glycidyl methacrylate- And at least one selected from the group consisting of water-releasing agents and carbodiimide-based agents.

The content of the unsaturated nitrile-aromatic vinyl-glycidyl methacrylate-based compatibilizing agent is 15% by weight or less, the content of the unsaturated nitrile-aromatic vinyl-maleic anhydride-based compatibilizing agent is 15% The diltiethacrylate-based compatibilizing agent may be contained in an amount of not more than 15% by weight, and the carbodiimide-based water-releasing agent may be contained in an amount of not more than 10% by weight.

The alkyl acrylate may be at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate have.

The unsaturated nitrile-aromatic vinyl-glycidyl methacrylate-based compatibilizer has a glass transition temperature of about 20 to about 200 DEG C, a weight average molecular weight of about 200 to about 300,000, and optionally an aromatic vinyl-glycidyl Methacrylate may be substituted.

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

The carbodiimide-based water-releasing agent may have a weight average molecular weight of about 50 to about 300,000, and may be represented by the following formula (4) or (5).

[Chemical Formula 4]

In 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 an aryl group having 6 to 36 carbon atoms.

[Chemical Formula 5]

In the above formula (5), C is carbon, N is nitrogen, R _c is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 36 carbon atoms, and n is an integer of 2 to 30,000.

In addition, the polymer resin composition according to one embodiment of the present invention can be used as a polymer resin composition in the form of a dye, a pigment, an impact modifier, a filler, a stabilizer, a lubricant, an antioxidant, an antimicrobial agent, ≪ RTI ID = 0.0 > and / or < / RTI >

As the antioxidant, for example, a phenol-based primary antioxidant, a phosphite-based secondary antioxidant, and a thioester-based antioxidant may be used. In this case, the phenolic primary antioxidant may have a weight average molecular weight of 50 to 300,000, and the phosphite antioxidant may be selected from the group consisting of, for example, the following formulas (6) to (8) The antioxidant may be a compound represented by the following formula (9) or (10).

[Chemical Formula 6]

In Chemical Scheme 6, O is oxygen and P is phosphorus, and _Rd and _Re are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms to be.

(7)

In Formula 7, O is oxygen and P is phosphorus, and _Rf and _Rg are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, n represents an integer of 1 or more as a substituted repeating unit.

[Chemical Formula 8]

R _h , R _i , R _j and R _k are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms or a substituted or unsubstituted alkyl group having 6 to 40 carbon atoms, Gt; is an unsubstituted aryl group.

[Chemical Formula 9]

[Chemical formula 10]

In the general formulas (9) and (10), C is carbon, O is oxygen and S is sulfur, and _Rm and _Rn are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms or a substituted or unsubstituted group having 6 to 40 carbon atoms Lt; / RTI >

The lubricant may be at least one selected from the group consisting of a metal stearate lubricant, an amide lubricant, a paraffin lubricant, and an ester lubricant.

The stabilizer may be a Halt light stabilizer, a benzotriazole light absorber or a benzophenone light absorber.

The pigment includes inorganic pigments such as carbon black, titanium oxide, zinc oxide, and iron oxide; Organic pigments including cyanine pigments, phosphorus pigments, quinone pigments, lerinon pigments, isoindolinone pigments, and thioindigo pigments, and the like.

Examples of the plasticizer include phthalic acid ester plasticizers such as diethyl phthalate, dioctyl phthalate and dicyclohexyl phthalate; Aliphatic dibasic acid ester plasticizers such as di-n-butyl adipate, di-n-octyl adipate, di-n-butyl sebacate and di-2-ethylhexyl azelate; Phosphate ester plasticizers such as diphenyl-2-ethylhexyl phosphate and diphenyloctyl phosphate; Tributyl acetyl citrate, tri-2-ethylhexyl acetyl citrate, tributyl citrate, and other hydroxycarboxylic acid ester plasticizers; Fatty acid ester plasticizers such as methyl acetyl ricinoleate and methyl stearate; Polyhydric alcohol ester plasticizers such as glycerin triacetate; Epoxidized fatty acid butyl esters, and epoxy-based plasticizers such as octyl stearate.

The organic-inorganic particles may include silica, colloidal silica, alumina, alumina sol, talc, titanium dioxide, mica, calcium carbonate, polystyrene, polymethylmethacrylate, or silicone. The particles are not limited to whether they are surface-treated, but when titanium dioxide or talc surface-treated is used, not only the whole physical properties including stiffness and impact strength are excellent but also the specific gravity, heat resistance and injection moldability are improved It is effective. Specifically, the surface treatment may be carried out by a chemical or physical method using a treating agent such as a silane coupling agent, a higher fatty acid, a metal salt of a fatty acid, an unsaturated fatty acid, an organic tinate, a resin acid or polyethylene glycol. The inorganic particles may have an average particle size of about 1 to about 30 mu m, preferably about 1 to about 15 mu m, and the heat resistance and rigidity are improved within the above range.

The nucleating agent may be a sorbitol-based metal salt, a phosphate-based metal salt, a quinacridone, a calcium carboxylate, an amide-based organic compound, or the like, preferably a phosphate-based metal salt.

According to another embodiment of the present invention, the polymer resin composition may have a tensile strength loss rate represented by the following general formula (1): about 0.5 to about 20%.

[Formula 1]

Tensile strength loss rate (%) = [(Tensile strength before test - Tensile strength after test) / Tensile strength before test] × 100

The pre-test tensile strength and the post-test tensile strength are measured as follows. The pellets prepared by uniformly kneading and extruding the polymeric resin composition were extruded at an injection temperature of about 250 ° C. and then extruded at a temperature of about 23 ± 2 ° C. and about 50 ± 5% And the chemical resistance test fixture was made to have a critical deformation amount of about 2.2%, and the specimen was fixed with the test fixture. Then, the aromatic / aliphatic chemical blend product or the UV screening agent was applied to the specimen for about 1 minute, Leave at 23 ± 2 ° C for about 72 hours, and then measure the tensile strength before and after the test. Wherein the aromatic / aliphatic chemical blend product comprises about 10 to 90% by weight of ethanol, and the aliphatic and aromatic alcohols, aliphatic and aromatic esters, aromatic aldehydes, unsaturated hydrocarbons, saturated hydrocarbons, aliphatic amines, aliphatic diamines, And at least one selected from the group consisting of terpine.

The polymer resin composition may have an excellent flame retardancy of V-0 or higher at 3.0 mm under UL 94 V Test (Vertical Burning Test).

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

< Example >

Butadiene-styrene (ABS) resin powder containing about 60% by weight of butadiene rubber, Resorcinol bis (diphenylphosphate) type flame retardant ((meth) acrylate) RDP) and bisphenol A bis (diphenylphosphate) flame retardant (BDP).

Production of polyester resin

[Manufacturing Example A]

(0.957 mol) of 1,4-cyclohexanedimethanol as diol component, 313 g (5.043 mol) of ethylene glycol and 105 g (0.718 mol) of isosorbide were charged into a flask equipped with a stirrer and an outlet condenser Were mixed in a 3 L reactor and the mixture was subjected to an esterification reaction at a temperature of 255 캜. At this time, the generated water was removed, and the mixture was transferred to a polycondensation reactor equipped with a stirrer, a cooling condenser and a vacuum system after the generation and the discharge of water were completed.

After the catalyst, the stabilizer and the coloring agent were added to the mixture, the temperature inside the reactor was raised to 265 ° C, the pressure was reduced to 50 mmHg, ethylene glycol was removed for 40 minutes, the pressure was reduced to 0.1 mmHg, Resin. The polyester resin thus produced had a weight average molecular weight (Mw) of 63,000 (g / mol) and an intrinsic viscosity of 0.76 (dl / g).

[Preparation Example B]

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

Preparation of Polymeric Resin Composition

Kneading extrusion was carried out uniformly at a cylinder temperature of 250 DEG C and a die temperature of 245 DEG C using a biaxial kneading extruder (?: 40 mm, L / D = 44) so as to obtain the compositions shown in Tables 1 and 2, To prepare a polymer resin composition.

Example
(Unit weight%) One 2 3 4 5 6 7 Polyester
Suzy Production Example A - 10 - - - - - Production Example B 60 30 20 37 20 35 50 PC - 20 40 60 40 50 35 20 SAN - - - - - - ABS - 8 8 8 8 18 18 18 Flame retardant RDP - 12 - 15 12 12 6 Flame retardant BDP 12 - 12 - - - 6

Comparative Example
(Unit weight%) One 2 3 4 5 6 7 Polyester
Suzy Production Example A - - - - - 10 - Production Example B - - - - - - 60 PC - 70 80 80 80 70 70 10 SAN - 12 - - - - - - ABS - 18 8 20 10 18 8 18 Flame retardant RDP - 12 - 10 - 12 6 Flame retardant BDP - - - - 12 - 6

< Experimental Example >

Tensile property test

A dog bone specimen having a size of (150 mm) × (12.7 mm) × (3.2 mm) according to the ASTM D638 standard was prepared using the polymer resin composition prepared in the above Examples and Production Examples, and then mounted on a Universal Test Mechine And tensile properties were measured.

In Tables 3 and 4 below, the terms related to tensile properties are as follows.

Tensile Strength (@Y): Tensile Strength at Yield Point

Tensile Elongation (@Y): Tensile elongation at yield point

Tensile Strength (@B): Tensile strength at breaking point

Tensile elongation at break (@B): Tensile elongation at break

Chemical resistance experiment

Dog bone-shaped specimens having a size of (150 mm) × (12.7 mm) × (3.2 mm) according to ASTM D638 were prepared using the polymer resin compositions prepared in the examples and preparation examples, The condition was adjusted for 24 hours under the condition of 50 ± 5% relative humidity, and evaluation was carried out according to the following method.

① The chemical resistance test fixture was fabricated with a critical strain of 2.2%, and the tensile specimen was fixed with the test fixture.

② An aromatic / aliphatic chemical blend product or UV screening agent was applied to the tensile specimen for 1 minute and left at 23 ± 2 ℃ for 72 hours.

(3) After 72 hours at 23 ± 2 ° C., the tensile strength before and after the test was measured, and the tensile strength loss rate (%) expressed by the following formula was measured to compare chemical resistance.

[Formula 1]

Tensile strength loss rate (%) = [(Tensile strength before test - Tensile strength after test) / Tensile strength before test] × 100

In the above, the aromatic / aliphatic chemical blend comprises 10 to 90% by weight of ethanol and further comprises at least one selected from the group consisting of the following components.

Detailed components: aliphatic and aromatic alcohols, aliphatic and aromatic esters, aromatic aldehydes, unsaturated hydrocarbons, saturated hydrocarbons, aliphatic amines, aliphatic diamines,

In addition, in the above, the UV screening agent is generally selected as a product to be distributed.

In the following Tables 3 and 4, the terms related to the tensile strength loss rate are as follows.

Tensile strength loss ratio (A): When an aromatic / aliphatic chemical blend of alcohol base is applied, the tensile strength loss rate

Tensile strength loss rate (B): When a UV blocking agent is applied, the tensile strength loss rate

Flexural properties  Experiment

Dog bone shaped specimens having dimensions of (127 mm) × (12.7 mm) × (6.4 mm) according to ASTM D740 standard were prepared using the polymer resin composition prepared in the above Examples and Preparation Examples, and then mounted on a Universal Test Mechine And the flexural properties were measured.

Impact property  Experiment

The specimen (3.2 T test piece, 3.2 T, RT) and (64.0 mm) × (12.7 mm) specimens (64.0 mm) × (12.7 mm) × 3.2 mm were prepared using the polymer resin composition prepared in the above- (6.4 T test piece, 6.4 T, RT) were respectively prepared and measured with an Izod impact strength measuring instrument at 23 ° C according to ASTM D256 standard.

Heat resistance experiment

A specimen having a size of (127 mm) × (13 mm) × (10 mm) was prepared using the polymer resin composition prepared in the above Examples and Production Examples, and the pressure applied to the specimen according to ASTM D648 standard was 0.455 MPa The heat distortion temperature (HDT) or heat distortion temperature (HDT) was measured.

Flammability test

(127 mm) × (12.7 mm) × (3.0 mm) size was produced by using the polymer resin composition prepared in the above Examples and Production Examples. Then, according to UL 94 V Test (Vertical Burning Test) Respectively.

The above evaluation results are summarized in Tables 3 and 4 below.

Example One 2 3 4 5 6 7 Tensile properties burglar
(@Y, Kgf / cm ²⁾ 34 57 72 50 72 60 46 Elongation
(@Y,%) 4.3 4.4 4.5 4.4 3.5 3.5 3.6 burglar
(@ B, Kgf / cm ² ) 385 414 295 380 389 360 338 Elongation
(@B,%) 5.6 2.0 8.2 2.0 9.6 3.7 9.9 Modulus of elasticity
(Kgf / cm ^{2 )} 20,666 23,521 22,332 23,302 20,360 19,690 19,018 The tensile strength
Loss rate A
(%) 3 5 10 5 8 5 4 B
(%) 4 6 13 6 11 5 5 Flexural properties burglar
(Kgf / cm ² ) 723 804 839 786 661 632 596 Modulus of elasticity
(Kgf / cm ² ) 20,242 22,348 23,122 22,248 20,142 19,150 18,299 Impact property 3.2T, RT
(J / m) 139 427 427 389 745 711 678 6.4 T, RT
(J / m) 715 698 757 554 432 447 432 Heat resistance ℃ 71 75 80 68 72 67 63 Flammability UL V V-0 V-0 V-0 V-0 V-0 V-0 V-0

Comparative Example One 2 3 4 5 6 7 Tensile properties burglar
(@Y, Kgf / cm ²⁾ 451 604 432 453 447 590 432 Elongation
(@Y,%) 5.2 4.7 5.7 5.6 5.5 4.8 3.5 burglar
(@ B, Kgf / cm ² ) 534 470 479 493 493 463 330 Elongation
(@B,%) 175.0 48.4 143.5 155.0 156.3 120.8 25.8 Modulus of elasticity
(Kgf / cm ^{2 )} 16,146 23,725 17,029 16,800 16,738 22,375 19,500 The tensile strength
Loss rate A
(%) 40 46 38 45 40 29 3 B
(%) 43 51 40 50 45 35 5 Flexural properties burglar
(Kgf / cm ² ) 649 873 611 620 621 823 587 Modulus of elasticity
(Kgf / cm ² ) 17,122 23,529 15,873 11,328 10,621 23,122 18,027 Impact property 3.2T, RT
(J / m) 427 424 608 556 530 420 663 6.4 T, RT
(J / m) 610 631 432 483 508 600 390 Heat resistance ℃ 112 87 117 116 115 72 58 Flammability UL V V-2 V-0 V-2 V-1 V-0 V-0 V-0

Referring to Tables 3 and 4, it can be seen that the embodiments of the present invention have improved chemical resistance and flame retardancy compared to the comparative example, while exhibiting excellent mechanical properties such as tensile properties, flexural properties, impact properties, and heat resistance .

Particularly, in the case of the examples, all of the flame retardancy evaluations were evaluated as V-0 grades, and it was confirmed that the flame retardancy was excellent. The tensile strength loss rate, which is an index indicating chemical resistance, was about 3 to 13% It can be confirmed that it is greatly improved.

In Comparative Example 7, the flame retardancy and the chemical resistance showed some similar results to those of the examples of the present application, but the polycarbonate resin was contained in a small amount, and the tensile property and flexural properties were relatively lowered , And the thermal deformation temperature was determined to be 60 DEG C or less as a critical point, so that the heat resistance was remarkably decreased.

Claims (17)

A polyester comprising a residue of a dicarboxylic acid component comprising terephthalic acid and a residue of a diol component comprising 5 to 60 mol% of isosorbide, 5 to 80 mol% of cyclohexanedimethanol and remaining amounts of other diol compounds 5 to 70% by weight of resin;
15 to 65% by weight of a polycarbonate resin; And
And 1 to 20% 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 a weight average molecular weight of 10,000 to 100,000 g / mol and a glass transition temperature of 50 to 200 ° C.
The polyester resin composition according to claim 1, wherein the dicarboxylic acid component of the polyester resin includes at least one selected from the group consisting of aromatic dicarboxylic acids having 8 to 20 carbon atoms and aliphatic dicarboxylic acids having 4 to 20 carbon atoms .
The polymer resin composition according to claim 1, wherein the diol component in the polyester resin comprises at least one member selected from the group consisting of compounds represented by the following formulas (1), (2) and (3)
[Chemical Formula 1]

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms; n ₁ and n ₂ are each independently an integer of 0 to 3; ,
(2)

In Formula 2, R ₅ , R ₆ , R _7, and R ₈ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,
(3)

In Formula 3, n ₃ is an integer of 1 to 7.
The polymer resin composition according to claim 1, wherein the flame retardant comprises at least one member selected from the group consisting of a halogen flame retardant, a phosphorus flame retardant, and an inorganic flame retardant.
The composition of claim 1, wherein the aromatic vinyl-unsaturated nitrile copolymer, the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, the alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, and the alkyl methacrylate- Silicone-alkyl acrylate graft copolymer. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The composition according to claim 7, further comprising an aromatic vinyl-unsaturated nitrile copolymer, an unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-diene rubber- And 1 to 25% by weight of at least one copolymer selected from the group consisting of silicone-alkyl acrylate graft copolymers.
8. The polymer resin composition according to claim 7, wherein the diene rubber is a butadiene rubber or an isoprene rubber.
The polymer resin composition according to claim 7, wherein the unsaturated nitrile is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, and? -Chloroacrylonitrile.
The method according to claim 7, wherein the aromatic vinyl is selected from the group consisting of styrene,? -Methylstyrene vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, By weight based on the total weight of the polymer resin composition.
8. The polymer resin composition according to claim 7, wherein the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer is an 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 copolymer.
8. The polymeric resin composition according to claim 7, wherein the alkyl methacrylate-silicone-alkyl acrylate graft copolymer is a methyl methacrylate-silicone-butyl acrylate graft copolymer.
The polymeric resin composition according to claim 1, which has a tensile strength loss rate of 0.5 to 20% represented by the following general formula (1)
[Formula 1]
Tensile strength loss rate (%) = [(Tensile strength before test - Tensile strength after test) / Tensile strength before test] × 100.
The polymer resin composition according to claim 1, having a flame retardancy of V-0 or higher at 3.0 mm under UL 94 V Test (Vertical Burning Test).
The image forming apparatus according to claim 1, wherein at least one selected from the group consisting of a dye, a pigment, an impact modifier, a filler, a stabilizer, a lubricant, an antioxidant, an antibacterial agent, a releasing agent, Further comprising an additive.