KR20160061745A - Polycarbonate composition improved infraredproof property and resin article - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition comprising a polycarbonate resin, an organic metal complex, and a complex metal oxide including at least three types of metals and tungsten, and to a resin molded product provided by using the resin composition. Provided in the present invention is the polycarbonate resin composition, having material properties such as excellent molding heat resistance, weather resistance, and scratch resistance.

Description

BACKGROUND OF THE INVENTION Field of the Invention [0001] The present invention relates to a polycarbonate resin composition,

The present invention relates to a polycarbonate resin composition and a resin molded article having improved light shielding. More particularly, the present invention relates to a polycarbonate resin composition having high light transmittance in the visible light region, high light ray shielding property in the infrared or near infrared region, and excellent physical properties such as heat resistance, weather resistance and scratch resistance, And a resin molded article produced using the polycarbonate resin composition.

Polycarbonate resins are used in various fields such as appearance of various building materials and electronic products, automobile interior and exterior materials, packaging materials, cases, boxes, and interior and exterior materials due to excellent properties such as impact resistance or heat resistance. In particular, polycarbonate resins are widely used in various fields due to their excellent mechanical properties and appearance due to high light transmittance.

However, when a polycarbonate resin is used for an automobile window member or a window member for a building, the temperature of the interior of the building or the inside of the automobile is greatly increased due to light having a wavelength in the infrared region which makes the user feel heat.

Previously, there has been known a method of adding a light shielding coating to the outside of a polycarbonate resin or adding an additive for shielding infrared rays to a polycarbonate.

For example, Korean Patent Laid-Open Publication No. 2004-0044541 discloses a method of applying inner ultraviolet and infrared ray coating on a polycarbonate substrate. However, according to this method, there is a limit to increase the manufacturing time and cost due to the coating process if a facility for the coating process is added. In addition, when the polycarbonate product is used for a long time, the outer coating is damaged and the light shielding performance is deteriorated.

Japanese Patent Laid-Open Publication No. 2009-505871 discloses a method of shielding light in an infrared ray region by mixing an inorganic additive with polycarbonate. However, when the inorganic additive is used, the appearance of the final molded resin article is degraded, There is a limit in that the solar radiation reaches the ground and the person can not effectively shield the light in the near-infrared wavelength region where the sensation temperature is high.

Japanese Laid-Open Patent Application No. 2008-208274 and Korean Patent Laid-Open No. 2003-0008521 disclose a method of adding a tungsten or tungsten composite oxide to polycarbonate. However, these methods are not suitable for visible light, There is a limit in which the degree of selective blocking of the light of the region wavelength is not sufficient.

Accordingly, there is a need to develop a method for selectively shielding the light of the infrared region wavelength, thereby lowering the sensation temperature and reducing energy consumption, while maintaining transparency and inherent physical properties of the polycarbonate resin itself.

Korean Patent Publication No. 2004-0044541 Japanese Patent Application Laid-Open No. 2009-505871 Japanese Patent Laid-Open No. 2008-208274 Korean Patent Publication No. 2003-0008521

The present invention is to provide a polycarbonate resin composition having high light transmittance in the visible light region, high light ray shielding property in the infrared or near infrared region, and excellent physical properties such as heat resistance, weather resistance and scratch resistance.

The present invention also provides a resin molded article produced using the polycarbonate resin composition.

In this specification, polycarbonate resin; An organometallic complex including a polymer binder resin and metal particles; And a composite metal oxide containing at least three metals selected from the group consisting of Al, Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs and tungsten. To provide a resin composition.

Further, in the present specification, a resin molded article comprising the polycarbonate resin composition is provided.

Hereinafter, the polycarbonate resin composition and the resin molded article according to the specific embodiment of the present invention will be described in detail.

According to one embodiment of the invention, a polycarbonate resin; An organometallic complex including a polymer binder resin and metal particles; And a composite metal oxide containing at least three metals selected from the group consisting of Al, Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs and tungsten. A resin composition may be provided.

The present inventors have found that a resin composition obtained by adding a composite metal oxide containing three or more kinds of specific metals together with the above tungsten and an organic metal composite including a polymeric binder resin and metal particles to a polycarbonate together, It is confirmed through experiments that the high light transmittance and high light ray shielding characteristics can be selectively provided in the infrared or near infrared region, and also the physical properties such as excellent molding heat resistance, weather resistance and scratch resistance can be secured. Respectively.

Since the polycarbonate resin composition includes an organometallic complex including a polymer binder resin and metal particles, it is possible to largely increase the rejection ratio for light rays in the infrared or near infrared region.

The polymer binder resin contained in the organic metal complex may include at least one polymer selected from the group consisting of polyolefin resins, polyamides, polycarbonates, polyesters and polyisobutylene. The polyolefin resin may be a polyethylene resin, a polypropylene resin, an ethylene-propylene copolymer, or an ethylene-alpha olefin copolymer.

But are not greatly limited, such as the specific physical properties of the polymer binder resin, such as from 50,000 to 500,000 may have, or of from 100,000 to 300,000 weight average molecular weight, or 0.870 g / cm ³ to 0.970 g / cm ^3, Or a density of 0.9 g / cm ³ to 0.95 g / cm ³ .

As the metal particles contained in the organic metal complex, aluminum or aluminum oxide may be used in order to further increase the charge ratio to the light in the infrared or near infrared region.

In the organometallic complex, the metal particles may be dispersed in the polymeric binder resin, or the binder resin may be coated on the surface of the metal particles.

The organometallic complex may include 50 to 500 parts by weight of the metal particles relative to 100 parts by weight of the polymeric binder resin.

The metal particles may have a maximum diameter of 1 탆 to 100 탆, or 10 탆 to 50 탆.

On the other hand, as the composite metal oxide includes at least three kinds of metals and tungsten among specific metals, it is more efficient to use a metal oxide containing one kind of metal other than tungsten oxide or tungsten, It is possible to secure a transmittance equal to or higher than that in the visible light region.

In the composite metal oxide, at least three metals selected from the group consisting of Al, Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs; tungsten; And oxygen may form covalent bonds with each other, or may form covalent bonds and coordination bonds.

Specifically, the composite metal oxide may include a compound represented by the following formula (1).

[Chemical Formula 1]

M1 _x1 M2 _x2 M3 _x3 W _y O _z

In Formula 1, M1 _, M2 _{, and} M3 may be the same or different from each other, and each of Al, Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb, <(x1 + x2 + x3) / y? 10.0, and 3.0 <z / y? 30.0.

(X1 + x2 + x3) / y may be a rational number greater than 1.0 and less than or equal to 10.0, and z / y may be a rational number greater than 3.0 but less than or equal to 30.0. In the above formula (1), x1, x2, x3, y and z mean the molar ratio of the corresponding element.

In the composite metal oxide represented by the above formula (1), the molar ratio (y) of tungsten with respect to M1 _, M2 And M3 may be 1.0 to 10.0 times, or 2.0 to 7.0 times as much as the sum (x1 + x2 + x3) of the number of moles of metal elements.

As described above, the M1 _, M2 And As the number of moles of the metal of M3 is 1.0 times or more, the polycarbonate resin composition can shield the light in the near infrared ray wavelength region more efficiently and secure the same level of transparency in the visible light region.

In the complex metal oxide of Formula 1, the number of moles (z) of oxygen atoms relative to the number of moles (y) of tungsten is 3.0 times or more, specifically 3.0 times to 30.0 times, or 8.0 times to 10.0 times.

On the other hand, in the above formula (1), 0. 0.1 < x1? 10.0, 0.1? X2? 10.0, 0.1? X3? 10.0 and 7.0? Z? 11.0. Specifically, each of x1, x2 and x3 may be 0.1 to 10.0 or 0.1 to 5.0 or 0.5 to 3.0.

More preferably, M 1, M 2 and M 3 in the formula (1) are Sn, Sb and Cs, respectively, and x 1, x 2 and x 3 are rational numbers in the range of 0.5 to 3, (x1 + x2 + x3) / y? 7.0 and 8.0? z / y? 10.0.

The composite metal oxide may be a longest diameter of 1 nm to 100 탆, or a fine particle having a longest diameter of 10 nm to 10 탆. If the maximum diameter of the composite metal compound is too small, the aggregation of the particles easily occurs, and the dispersibility in the resin composition may be greatly lowered. If the maximum diameter of the composite metal compound is too large, the appearance or mechanical properties of the polycarbonate resin composition of the embodiment may be deteriorated or the haze value may be greatly increased.

The polycarbonate resin composition of one embodiment may contain 0.00001 to 0.5 parts by weight of the composite metal oxide and 0.0001 to 0.1 part by weight of the organometallic complex relative to 100 parts by weight of the polycarbonate resin.

If the content of each of the composite metal oxide and the organometallic complex relative to the polycarbonate resin is too low, the polycarbonate resin composition and the molded article produced therefrom may not have sufficient light shielding ability and the light rays in the infrared or near- The shielding properties may also be insufficient.

If the content of each of the composite metal oxide and the organometallic complex relative to the polycarbonate resin is too high, the light transmittance of the final product may be significantly lowered or opaque.

The concrete examples of the polycarbonate resin included in the polycarbonate resin composition of one embodiment are not limited to a wide range. The polycarbonate resin may be used in a variety of building materials and electronic products, automobile interior and exterior materials, packaging materials, cases, boxes, interior and exterior materials A polycarbonate resin known to be capable of being used can be used.

Specifically, the polycarbonate resin included in the polycarbonate resin composition of one embodiment may have a weight average molecular weight of 1,000 to 300,000, or 10,000 to 150,000.

The process for synthesizing the polycarbonate is not particularly limited, and can be obtained, for example, by reacting a divalent phenol with a carbonate precursor. Specific examples of such a synthesis method include an interfacial polymerization method, a melt ester exchange method, a solid-state ester exchange method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Representative examples of the divalent phenol include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis (4-hydroxy- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) cyclohexane, 1,1- 4,4'- (m-phenylene diisopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfoxide, bis Phenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2- Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9- Fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

Specific examples of the carbonate precursor include carbonyl halide, carbonic acid diester or haloformate, and specific examples thereof include phthalic acid, diphenyl carbonate, and dihaloformate of dihydric phenol.

In the production of the polycarbonate resin by the interfacial polymerization method between the dihydric phenol and the carbonate precursor, an antioxidant for preventing oxidation of the catalyst, the terminal terminator and the dihydric phenol may be used if necessary.

The polycarbonate resin may be a branched polycarbonate resin copolymerized with a polyfunctional aromatic compound having three or more functional groups, a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (alicyclic) bifunctional carboxylic acid, a bifunctional alcohol And a polyester carbonate resin obtained by copolymerization of such a bifunctional carboxylic acid and a bifunctional alcohol, or a mixture of two or more thereof.

Examples of the trifunctional or higher polyfunctional aromatic compound include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl- Can be used.

The aliphatic bifunctional carboxylic acid is preferably a, w-dicarboxylic acid. The aliphatic bifunctional carboxylic acid includes, for example, a linear saturated aliphatic dicarboxylic acid such as sebacic acid (decane diacid), dodecane diacid, tetradecanedioic acid, octadecanedioic acid, And alicyclic dicarboxylic acids such as benzoic acid, benzoic acid, benzoic acid, benzoic acid, and the like. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

The reaction by the interfacial polymerization method is a reaction between bifunctional phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. Examples of the acid coupling agent include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and pyridine.

As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. For promoting the reaction, for example, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. As the molecular weight regulator, monofunctional phenols such as phenol, p-tert-butylphenol, p- Is preferably used. Examples of the monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol. These monofunctional phenols having an alkyl group having a relatively long chain are effective when improvement in fluidity and hydrolysis resistance is required.

The reaction temperature in the interfacial polymerization method may be usually from 0 to 40 ° C, the reaction time is preferably from several minutes to 5 hours, and the pH during the reaction is preferably kept at 10 or more.

On the other hand, the reaction by the melting method is a transesterification reaction of a dihydric phenol and a carbonic acid diester, and the reaction is carried out at 120 to 350 ° C under reduced pressure, in the presence of an inert gas, by mixing the dihydric phenol and the carbonic acid diester. The decompression degree is changed stepwise, and finally, the pressure is reduced to 133 Pa or less to remove the generated phenol from the system. The reaction time is usually about 1 to 4 hours.

Specific examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate, among which diphenyl carbonate is preferable.

A polymerization catalyst may be used to accelerate the polymerization rate in the polycarbonate synthesis process. Examples of the polymerization catalyst include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, hydroxides of boron and aluminum, alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, alkoxides of alkali metals and alkaline earth metals, A catalyst used for esterification reaction or ester exchange reaction such as an organic acid salt of an alkaline earth metal, a zinc compound, a boron compound, a silicon compound, a germanium compound, an organotin compound, a lead compound, an antimony compound, a manganese compound, a titanium compound, . The polymerization catalyst may be used alone or in combination of two or more. The amount of the polymerization catalyst, the two of the material with respect to 1 mole of phenol, preferably from 1 * ^0-9 * ^0-5 to 1 equivalent, more preferably from 1 to 5 * ^0-8 * 0 ^{- 6} eq. Lt; / RTI &gt;

Further, in the above polymerization reaction, in order to reduce the phenolic end group, after the end or the end of the polycondensation reaction, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycar Phenylphenyl phenyl carbonate, and the like can be added.

In the above-mentioned molten ester exchange method, it is preferable to use an activator which neutralizes the activity of the catalyst. The amount of such an activator is preferably 0.5 to 50 mol per 1 mol of the remaining catalyst. The proportion of the aromatic polycarbonate after polymerization is preferably 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm. Examples of the deactivation agent include a phosphonium salt such as tetradecylbenzyl sulfonate tetrabutylphosphonium salt and an ammonium salt such as tetraethylammonium dodecylbenzylsulfate.

Meanwhile, the polycarbonate resin composition of one embodiment may further include an ultraviolet absorber.

The ultraviolet absorber means a compound that blocks ultraviolet energy or selectively absorbs ultraviolet energy to release it as other types of energy that are not harmful to the polymer, or inhibits the photoreaction of the polymer, in particular, the initiation of photodecomposition. The components or compounds which can be used are not limited.

Specific examples of the ultraviolet absorber include 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (3-tert- butyl- Benzo [b] thiazole, 2- [2-hydroxy-3,5-bis (a, a-dimethylbenzyl) phenyl] Triazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine- And mixtures of two or more species.

The ultraviolet absorber may include 0.0005 parts by weight to 1 part by weight based on 100 parts by weight of the polycarbonate resin. When the content of the ultraviolet absorber is within the above range, weather resistance of the resin composition and the molded article can be improved without causing bleeding of the ultraviolet absorber on the surface of the molded article and deterioration of mechanical properties of various molded articles.

The polycarbonate resin composition of one embodiment may further include at least one additive selected from the group consisting of a hindered amine light stabilizer, a releasing agent, an epoxy compound, a heat stabilizer and an antioxidant.

Examples of the hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl- Piperidyl) sebacate, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6- (2,2,6,6-tetramethyl-4-piperidyl) imino]], N, N'-bis (3-amino Propyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidylamino) -6-chloro-1,3,5-tri Azine condensate, dibutylamine-1,3,5-triazine-N, N'-bis (2,2,6,6) -tetramethyl-4-piperidyl-1,6-hexamethylenediamine and And a polycondensation product of N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, or a mixture of two or more thereof.

The hindered amine light stabilizer may be used in an amount of 0.001 part by weight to 1 part by weight based on 100 parts by weight of the polycarbonate resin. When the hindered amine light stabilizer is used in the above range, the polycarbonate resin composition of the present invention can be molded without causing deterioration of the mechanical properties of various kinds of molded articles and bleeding of the hindered amine light stabilizer on the surface of the polycarbonate resin composition. It is possible to improve the weather resistance of the molded article.

Meanwhile, the polycarbonate resin composition of one embodiment may further include a release agent to increase the productivity at the time of extrusion and injection, and to reduce the defective rate.

Examples of the release agent include higher fatty acid esters of higher fatty acids, mono- or polyhydric alcohols, natural animal waxes such as beeswax, natural plant waxes such as carnauba wax, natural petroleum waxes such as paraffin wax, natural coal waxes such as montan wax , An olefin wax, a silicone oil, an organopolysiloxane, or a mixture of two or more thereof.

Examples of the higher fatty acid esters include substituted or unsubstituted monovalent or polyhydric alcohols having 1 to 20 carbon atoms, and substituted or unsubstituted partial esters or esters of saturated fatty acids having 10 to 30 carbon atoms. Examples of the partial esters or all esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearic acid stearate, Propyleneglycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl lauroyl stearate, isopropyl palmitate, butyl stearate, methyl stearate, Isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, ethylene glycol distearate, and the like.

Examples of the higher fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid, and the like.

The release agent may be used in an amount of 0.0001 part by weight to 0.01 part by weight based on 100 parts by weight of the polycarbonate resin.

Meanwhile, the polycarbonate resin composition of one embodiment may further include an epoxy compound to further improve the hydrolysis resistance of the molded article to be produced.

Specific examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allyl glycidyl ether, t-butylphenylglycidyl ether, 3,4-epoxycyclohexylmethyl-3 Epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexyl Methyl-3 ', 4'-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) butyl-3', 4'-epoxycyclohexylcarboxylate, Cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylcyclohexylcarboxylate, bisphenol A diglycidyl ether , Tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis -Epoxy dicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butatadienedepoxide, tetraphenylethylene epoxide, octyl epoxidarate, epoxidized polybutadiene, 3,4 Dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl- Dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl- Butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl- -Epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,5-epoxy anhydride tetrahydrophthalate , 3-t-butyl-4,5-epoxy anhydrous tetrahydrophthalic acid, diethyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di- -4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, and the like.

The epoxy compound may be used in an amount of 0.0001 part by weight to 5 parts by weight based on 100 parts by weight of the polycarbonate resin. By using the epoxy compound in the above range, the hydrolysis resistance of the molded article can be improved without causing deterioration of the mechanical properties of bleeding of the epoxy compound on the surface of the molded article and various molded articles.

The polycarbonate resin composition of one embodiment may further include a heat stabilizer to prevent the molecular weight of the resin molded article from being lowered and the color from deteriorating. Specific examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and esters thereof. Specific examples of the heat stabilizer include triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenyl (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-di-tert-butylphenylphenylphosphite, monodecyldiphenylphosphite, monohexyldiphenylphosphite, Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearate (bis (2,4-di-tert- butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis &Lt; RTI ID = 0.0 &gt; tributyl But are not limited to, tetrakis (triphenylphosphine), tetrakis (triphenylphosphine), triphenylphosphate, triphenylphosphate, diphenylmonortalkenylphosphate, dibutylphosphate, dioctylphosphate, diisopropylphosphate, 4,4'- , 4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropylene benzenephosphate, or a mixture of two or more thereof.

The heat stabilizer may be used in an amount of 0.0001 part by weight to 1 part by weight based on 100 parts by weight of the polycarbonate resin. As the stabilizer is used in the above amount, the molecular weight of the resin and discoloration of the resin can be prevented without causing bleeding of the additive.

In addition, the polycarbonate resin composition of one embodiment may further include a conventionally known antioxidant. Specific examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearyl thiopropionate, tri Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3-hydroxyphenyl) propionate, pentaerythritol tetrakis Butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert- ) Benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert- -Diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate , 4,4'-biphenylene diphosphine tetrakis (2,4-di-tert-butylphenyl), 3,9-bis {1,1- -4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane or a mixture of two or more thereof.

The antioxidant may be used in an amount of 0.0001 part by weight to 1 part by weight based on 100 parts by weight of the polycarbonate resin.

Meanwhile, the polycarbonate resin composition of one embodiment may further include a polymer resin other than the polycarbonate resin for the purpose of further improving and adjusting molding processability and various physical properties.

Specifically, the polycarbonate resin composition of one embodiment may further include at least one other polymer resin selected from the group consisting of a polyester resin, polyether, polyamide, polyolefin, and polymethyl methacrylate. The other polymer resin may be further contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polycarbonate resin.

On the other hand, the production method of the polycarbonate resin composition of the embodiment is not particularly limited, and a method and apparatus which are usually used in the production of the polymer resin composition and the like can be used without limitation.

Specifically, the polycarbonate resin composition of one embodiment may be prepared by melt-kneading the respective components contained therein. Specific examples of the melt kneading include a Banbury mixer, a kneading roll, and an extruder. Among them, an extruder is preferable in terms of kneading efficiency, and a multiaxial extruder such as a twin screw extruder is preferable.

A more preferable embodiment of the twin-screw extruder is as follows. For the screw shape, 1-line, 2-line, and 3-line screw screws can be used. As the extruder, those having a vent which can degas moisture in the raw material or volatile gas generated from the melt-kneaded resin can be preferably used. It is also possible to dispose a screen for removing foreign matter or the like mixed in the extrusion raw material in a zone in front of the extruder dice portion and to remove the foreign substance from the resin composition. Examples of the screen include a wire mesh, a screen changer, a sintered metal plate (disk filter, etc.), and the like.

The resin composition thus obtained may be produced in the form of pellets, and then various products may be produced by injection molding. In such injection molding, injection molding, injection press molding, gas assist injection molding, foam molding (including injection of supercritical fluid), insert molding, Molded articles can be obtained by injection molding such as injection molding, extrusion molding, hot-wall molding, rapid cooling molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The molding can be either a cold runner type or a hot runner type.

The resin composition may be used in the form of various shaped extrusion molded articles, sheets or films by extrusion molding. In addition, inflation, calendering, casting, and the like can be used for forming sheets and films. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation.

The resin composition may be formed into a molded article by rotary molding or blow molding. By the molding process, it is possible to obtain a molded article excellent in transparency and excellent in designability while having an infrared shielding ability.

According to another embodiment of the present invention, a resin molded article comprising the polycarbonate resin composition may be provided.

The resin molded article means an article obtained by molding the polycarbonate resin composition of one embodiment described above.

The resin molded article is preferably transparent depending on the properties required in the field of use. The transparency of such a resin molded article can be evaluated by the total light transmittance in the visible light region of the resin molded article, and it is preferable that the visible light transmittance is high.

The resin molded article of this embodiment can realize high infrared and near infrared ray rejection rates, i.e., low infrared ray and near infrared ray transmittance. Specifically, the resin molded article of the embodiment can have an infrared ray and a near-infrared ray transmittance of 30% or less, or 15% or less at a thickness of 3 mm.

The specific use of the resin molded article is not limited, and may be used as a window pane for a vehicle, a window pane for a building, and the like.

The resinous product of the embodiment can be subjected to various surface treatments. The surface treatment is to form a new layer on the surface layer of a resin molded article such as vapor deposition (physical vapor deposition and chemical vapor deposition), plating (electroplating, electroless plating, and hot dip galvanizing), coating, A method used for an ordinary polycarbonate resin can be applied.

Specific examples of the surface treatment include various surface treatments such as hard coat, water-repellent coat, oil-resistant coat, ultraviolet absorbent coat, infrared absorbent coat, and metalizing (typified by vapor deposition).

According to the present invention, it is possible to provide a resin composition which is excellent in heat resistance, weather resistance, and scratch resistance, combining infrared ray and ultraviolet ray shielding performance even with a polycarbonate substrate without additional coating, by mixing infrared rays and ultraviolet ray blocking agent having thermal stability on polycarbonate And a molded article comprising the same can be obtained.

INDUSTRIAL APPLICABILITY The resin composition and molded articles thereof of the present invention are useful for various uses such as windowpanes for vehicles, lamps for vehicles, and windowpanes for building materials.

Fig. 1 shows a graph of the transmittance of the resin molded article obtained in Example 1. Fig.
Fig. 2 is a graph showing the transmittance of the resin molded article obtained in Example 2. Fig.
3 is a graph showing the transmittance of the resin molded article obtained in Comparative Example 1. Fig.
4 is a graph showing the transmittance of the resin molded article obtained in Comparative Example 2. Fig.
5 is a graph showing the transmittance of the resin molded article obtained in Comparative Example 3. Fig.
6 shows SEM photographs of the composite metal oxides used in Examples 1 and 2, respectively.
7 is a SEM photograph of the organometallic complex used in Examples 1 and 2, respectively

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Synthetic example : Synthesis of polycarbonate resin>

1.0 mol of 2,2-bis- (4-hydroxyphenyl) propane, 1.05 mol of diphenyl carbonate and potassium hydroxide as a polymerization catalyst were fed into the reactor. Thereafter, the temperature in the reactor was slowly increased from 200 ° C to 300 ° C, and the condensation reaction proceeded while slowly lowering the pressure to about 0 torr at about 760 torr to synthesize a polycarbonate polymer (yield: 92.5%).

< Example  And Comparative Example : Preparation of polycarbonate resin composition &gt;

Example 1  And 3

(1) Production of resin pellets

The polycarbonate resin organic metal complexes and composite metal oxides obtained in the above Synthesis Example were mixed using a blender at the component ratios shown in Table 1, and then melt-kneaded using a vent type single screw extruder to produce resin pellets. At this time, the extrusion conditions were a discharge rate of 15 kg / h, a screw rotation rate of 150 rpm, and an extrusion temperature of 280 캜 to 300 캜.

(2) Production of Resin Molded Parts (Production of Specimen)

Using the hot-air dryer, the resin pellets obtained above were dried at 100 DEG C for about 4 hours. Then, the dried resin pellets were injected into a specimen having a thickness of 3.2 mm by applying a mold temperature condition of 300 DEG C and a mold temperature using a specimen injection machine.

Comparative Example 1  To 3

(1) Production of resin pellets

Resin pellets were prepared in the same manner as in Example 1, except that WO ₃ was used in place of the composite metal oxide in the ratio shown in Table 1 below.

(2) Production of Resin Molded Parts (Production of Specimen)

Using the resin pellets obtained above, the specimens of 3.2 mm thickness were injected in the same manner as in Example 1.

< Experimental Example : Evaluation of physical properties of resin molded article>

Experimental Example 1 : Near-infrared transmittance and measurement

The transmittance of the molded resin articles obtained in Examples 1 to 2 and Comparative Examples 1 to 3 was measured at a wavelength of 400 to 1300 nm using a UV-3600 model manufactured by Shimadzu Co. The transmittance changes according to wavelengths thereof are shown in FIGS. 1 to 5 .

Then, from the results of the transmittance measurement, the transmittance of 800 to 1300 nm band was measured and integrated to determine the near infrared ray transmittance. Further, in the result of the transmittance measurement, the transmittance of 380 to 750 nm was measured, and the transmittance was quantified as the visible light transmittance.

Experimental Example 2 : Hayes  Measure

The haze of the resin molded articles obtained in Examples 1 to 2 and Comparative Examples 1 to 3 was measured according to ASTM D 1003 using a measuring instrument of NDH-5000 model manufactured by Nippon Denshoku.

The compositions of the above Examples and Comparative Examples and the results of Experimental Examples 1 to 2 are shown in Table 1.

division unit Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 ingredient Polycarbonate Weight portion 100 100 100 100 100 SnSb ₂ Cs ₂ WO ₉ 0.02 0.02 0 0 0 Organometallic complex
(Al / Olefin) 0.003 0.006 0 0 0 WO ₃ 0 0 0.005 0.01 0.02 Piece Evaluation NIR transmittance % 27.6 10.3 92.1 89.3 81.4 Visible light transmittance % 50.4 34.2 90.6 83.3 69.4 Hayes % 25.4 37.1 4.31 7.76 14.23

- the organometallic complex used a product comprising 20 wt% of polyethylene having a density of about 0.920 g / cm &lt; ³ &gt; and 80 wt% of aluminum particles having a maximum diameter of about 20 mu m (specific SEM photographs are shown in Fig. 7 )

As shown in Table 1, the resin molded articles obtained in Examples 1 and 2 exhibited visible light transmittances of 40% or more, or 50% or more, and could shield light of near infrared wavelengths of 70% or more or 85% The point was confirmed.

3 and 5, which are graphs of the transmittance of resin molded articles of FIGS. 1 and 2 and Comparative Examples 1 to 3, which are graphs of transmittance of resin molded articles of Examples 1 and 2, It can be confirmed that the transmittance of the resin molded article is significantly lowered in the near infrared region of 800 nm to 1300 nm, effectively blocking near infrared and infrared region wavelengths.

On the contrary, in the case of the resin molded articles obtained in Comparative Examples 1 to 3, it was confirmed that the near infrared ray shielding ratio was only about 19% at the maximum, and the haze property was also higher than that of the resin molded articles of the Examples.

Claims (19)

Polycarbonate resin;
An organometallic complex including a polymer binder resin and metal particles; And
And a composite metal oxide containing at least three metals selected from the group consisting of Al, Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs and tungsten. Composition.
The method according to claim 1,
Wherein the polymeric binder resin comprises at least one polymer selected from the group consisting of a polyolefin resin, a polyamide, a polycarbonate, a polyester, and a polyisobutylene.
Polycarbonate resin composition.
The method according to claim 1,
Wherein the metal particles contained in the organic metal complex include aluminum or aluminum oxide.
The method according to claim 1,
Wherein the organometallic complex comprises 50 to 500 parts by weight of the metal particles relative to 100 parts by weight of the polymeric binder resin.
The method according to claim 1,
Wherein the metal particles have a longest diameter of 1 占 퐉 to 100 占 퐉.
The method according to claim 1,
0.00001 to 0.5 parts by weight of the composite metal oxide and 0.0001 to 0.1 part by weight of the organometallic complex relative to 100 parts by weight of the polycarbonate resin.
The method according to claim 1,
Wherein the polycarbonate resin has a weight average molecular weight of 1,000 to 300,000.
The method according to claim 1,
Wherein the composite metal oxide comprises a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
M1 _x1 M2 _x2 M3 _x3 W _y O _z
In Formula 1, M1 _, M2 _{, and} M3 may be the same or different from each other, and may be Al, Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb,
1.0 < (x1 + x2 + x3) / y? 10.0,
3.0 &lt; z / y &amp;le; 30.0.
9. The method of claim 8,
In Formula 1,
0. 0.1 < x1? 10.0, 0.1? X2? 10.0, 0.1? X3? 10.0, and 7.0? Z? 11.0.
9. The method of claim 8,
In Formula 1,
M1, M2 and M3 are Sn, Sb and Cs, respectively,
x1, x2 and x3 are rational numbers in the range of 0.5 to 3, respectively,
2.0? (X1 + x2 + x3) / y? 7.0,
8.0? Z / y? 10.0.
The method according to claim 1,
Wherein the composite metal oxide is fine particles having a longest diameter of 1 nm to 100 탆.
The method according to claim 1,
A polycarbonate resin composition further comprising an ultraviolet absorber.
13. The method of claim 12,
The ultraviolet absorber may be selected from the group consisting of 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (3-tert- butyl- Benzotriazole, 2 - [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H- , 2'-methylenebis (4-cumyl-6-benzotriazolephenyl) and 2,2'-p-phenylenebis (1,3-benzoxazine-4-one) Wherein the polycarbonate resin composition is a polycarbonate resin composition.
13. The method of claim 12,
And 0.0005 parts by weight to 1 part by weight of the ultraviolet absorber relative to 100 parts by weight of the polycarbonate resin.
The method according to claim 1,
Wherein the polycarbonate resin composition further comprises at least one additive selected from the group consisting of a hindered amine light stabilizer, a releasing agent, an epoxy compound, a heat stabilizer and an antioxidant.
The method according to claim 1,
Wherein the polycarbonate resin composition further comprises at least one other polymer resin selected from the group consisting of a polyester resin, a polyether, a polyamide, a polyolefin, and a polymethyl methacrylate.
A resin molded article comprising the polycarbonate resin composition of claim 1.
18. The method of claim 17,
A resin molded article having a thickness of 3 mm and an infrared and near-infrared transmittance of 30% or less
18. The method of claim 17,
Resin molded articles used as vehicle window members or building window members.

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