KR101614855B1 - Multilayer polycarbonate sheet - Google Patents

Abstract

The present invention relates to a multilayer polycarbonate sheet comprising a base layer including polycarbonate resin and an ultraviolet absorber; and a coating layer formed on at least one surface of the base layer, and including polycarbonate resin, an ultraviolet absorber, and complex metal oxide having three or more kinds of metals selected from the group consisting of Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs. Provided in the present invention is the multilayer polycarbonate sheet having high light transmittance in a visible ray area, having excellent light blocking properties in an infrared ray and near infrared ray area, having high heat resistance, weather resistance, and scratch resistance.

Description

[0001] MULTILAYER POLYCARBONATE SHEET [0002]

The present invention relates to a multilayer polycarbonate sheet. More specifically, the present invention relates to a multilayer polycarbonate sheet having high light transmittance in the visible light region, excellent light shielding property in the infrared and near infrared region, and high heat resistance, weather resistance, and scratch resistance.

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.

The present invention is to provide a multilayer polycarbonate sheet having high light transmittance in the visible light region, excellent light shielding property in the infrared and near infrared region, and high heat resistance, weather resistance and scratch resistance.

In the present specification, a substrate layer containing a polycarbonate resin and an ultraviolet absorber; And at least one member selected from the group consisting of polycarbonate resin, ultraviolet absorber and Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs, And a coating layer containing a composite metal oxide including at least a metal and tungsten. The multilayer polycarbonate sheet includes:

A multilayer polycarbonate sheet according to a specific embodiment of the present invention will be described in detail below.

According to one embodiment of the invention, a substrate layer comprising a polycarbonate resin and an ultraviolet absorber; And at least one member selected from the group consisting of polycarbonate resin, ultraviolet absorber and Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs, Or more of a metal and a composite metal oxide including tungsten, may be provided on the surface of the multilayer polycarbonate sheet.

The present inventors have found that the use of the above-mentioned specific multilayer polycarbonate sheet enables high light-shielding properties selectively in the infrared or near-infrared region while having high light transmittance in the visible light region, excellent molding heat resistance, weather resistance and scratch resistance And the like can be obtained together with the experiment.

Particularly, the multilayer polycarbonate sheet is a multilayer polycarbonate sheet comprising three layers selected from the group consisting of Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs in a coating layer containing a polycarbonate resin and an ultraviolet absorber It is possible to more effectively shield the light in the near infrared ray region and ensure the same level of transparency in the visible ray region, and at the same time, By forming the coating layer on one surface to improve durability and weather resistance, the multilayer polycarbonate sheet can be stably protected even when exposed to an external environment for a long period of time.

The multilayer polycarbonate sheet may include a coating layer formed on at least one side of the substrate layer.

Specifically, the base layer includes an ultraviolet absorber together with a polycarbonate resin, and can protect the polycarbonate resin from harmful effects due to ultraviolet rays in the atmosphere. The coating layer may contain at least one of an ultraviolet absorber and at least three metals selected from the group consisting of Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs and tungsten The present invention relates to a multilayer polycarbonate sheet for protecting the polycarbonate resin from harmful effects caused by ultraviolet rays in the air by means of an ultraviolet absorber and shielding the infrared ray through the composite metal oxide, It is possible to lower the sensation temperature and reduce energy consumption.

The multilayer polycarbonate sheet may include at least one of the base layer and the cover layer, and may include a coating layer formed on one side or both sides of the base layer. By forming the coating layer on at least one surface of the substrate layer, direct ultraviolet contact with the polycarbonate resin contained in the substrate layer can be minimized by the ultraviolet and infrared shielding effect of the coating layer. As a result, the yellowing of the polycarbonate resin due to the direct UV contact can be prevented, and the weather resistance of the multilayer polycarbonate sheet can be improved as well.

The ratio of the thickness of the base layer to the thickness of the coating layer may be from 5: 1 to 100: 1, or from 10: 1 to 80: 1, or from 20: 1 to 50: The ratio of the thickness of the base layer and the thickness of the coating layer can be calculated, for example, as a ratio of the total thickness of the coating layer to the thickness of the base layer when the coating layer is present on both surfaces of the base layer. When there is a covering layer between two or more base layers and a neighboring base layer among the base layers, the thickness of the base layer and the thickness of the covering layer are calculated through the sum of all the base layer thicknesses and the total thicknesses of all coating layers .

As the ratio of the thickness of the base layer and the thickness of the coating layer satisfies the above-mentioned ratio, the weatherability of the multilayer polycarbonate sheet and the infrared ray shielding effect can be increased. When the ratio of the thickness of the base layer to the thickness of the coating layer is less than 5: 1 and the thickness ratio of the coating layer is excessively increased, the visible light transmittance of the multilayer polycarbonate sheet is decreased, can do.

The thickness of the base layer and the coating layer may be determined according to the properties and use of the multilayer polyester sheet and is not particularly limited. For example, the thickness of the coating layer may be 0.01 mm to 1 mm, or 0.01 mm to 0.5 mm , Or 0.02 mm to 0.1 mm. Further, the thickness of one base layer may be 0.05 mm to 10 mm, or 1 mm to 8 mm, or 2 mm to 5 mm. Further, the thickness of the multilayer polycarbonate sheet may be 0.06 mm to 20 mm, or 1 mm to 11 mm, or 1.5 mm to 6 mm.

Examples of the method for producing the substrate layer and the coating layer are not limited to a great degree, but for example, a method of producing a polycarbonate resin pellet and molding the polycarbonate resin pellet can be used.

Examples of the method of molding the polycarbonate resin pellets are not limited to a wide range. For example, injection molding, injection press molding, gas assist injection molding, foam molding (including injection of supercritical fluid) An injection molding method such as molding, in-mold coating molding, heat insulating mold molding, rapid heating cooling mold molding, two-color molding, sandwich molding, and ultra high speed injection molding can be used. The molding can be either a cold runner type or a hot runner type. Preferably, it can be produced in the form of a sheet or a film through the above-mentioned molding method.

Examples of the method for producing the polycarbonate resin pellets include a method in which the resin composition extruded from an extruder is directly cut into pellets or strands are formed and then the strands are cut into pelletizers and pelletized.

The method of forming the coating layer on at least one surface of the base layer is not limited to a great degree, but a coextrusion method can be used, for example. Examples of the co-extrusion method include a method of joining the substrate layer and the coating layer pushed out from two or more extruders at a roll or a method of pneumatic shipment using a single extrusion die using a multi-nozzle.

On the other hand, the coating layer included in the multilayer polycarbonate sheet includes at least three metals selected from the group consisting of Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs and tungsten Composite metal oxides. The composite metal oxide is excellent in thermal stability as an infrared absorbent and a near infrared absorbent, and can improve the light shielding property against the infrared rays and near infrared rays of the multilayer polycarbonate sheet, and can greatly reduce the yellowing phenomenon.

In the composite metal oxide, at least three metals selected from the group consisting of 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 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.

In the formula 1, 0.1 < x1 < 10.0, 0.1 < x2 &lt; 10.0, 0.1 &lt; x3 &lt; 10.0 and 7.0 & 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 coating layer may contain 0.00001 to 1 part by weight, or 0.0001 to 0.5 part by weight of the composite metal oxide, based on 100 parts by weight of the polycarbonate resin.

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 50 탆. If the maximum diameter of the composite metal compound is too small, aggregation between the particles may easily occur and the dispersibility may be deteriorated. If the maximum diameter of the composite metal compound is too large, the haze value of the polycarbonate increases, which limits application of the multilayer polycarbonate sheet.

The method for producing the composite metal oxide is not limited to a specific method. For example, a method of mixing the reactants, followed by heat treatment in an inert atmosphere, and heat treatment in a reducing atmosphere may be used.

The hydrate powder of tungsten oxide obtained by dissolving tungsten trioxide powder, tungsten dioxide powder, hydrate of tungsten oxide, tungsten hexachloride powder, ammonium tungstate powder and tungsten hexachloride in alcohol and drying the mixture is used as the reactant . It is also possible to use a hydrate powder of tungsten oxide obtained by dissolving tungsten hexachloride in alcohol, precipitating by adding water, and drying it. Further, a tungsten compound powder obtained by drying an aqueous solution of ammonium tungstate can be used.

Examples of the compounds containing the M1, M2 and M3 elements include chloride salts, nitrates, sulfates, oxalates, oxides, carbonates and hydroxides of M1, M2 and M3 elements, Solution, and more preferably, the use of a carbonate and a hydroxide is safe in the process because no harmful gas or the like is generated.

The heat treatment conditions of the composite tungsten oxide fine particles in an inert atmosphere are preferably 600 DEG C or higher. The starting material heat-treated at 600 ° C or higher has a sufficient near infrared ray shielding power and is efficient as infrared shielding fine particles. In order to secure an inert atmosphere, it is preferable to spray a gas such as Ar or N ₂ .

As the heat treatment conditions in the reducing atmosphere, the starting material is first heat-treated at a temperature of 100 ° C or higher and 850 ° C or lower in a reducing gas atmosphere, and then heat-treated at a temperature of 650 ° C or higher and 1200 ° C or lower in an inert gas atmosphere. The reducing gas at this time is not particularly limited, but H ₂ is preferable. When H ₂ is used as the reducing gas, the composition of the reducing atmosphere is preferably 0.1% or more, and more preferably 2% or more, in terms of the volume ratio of H ₂ .

On the other hand, the concrete examples of the polycarbonate resin contained in the base layer and the coating layer are not limited to a wide range, and can be used in various building materials and exterior of electronic products, automobile interior and exterior materials, packaging materials, cases, boxes, interior and exterior materials For example, a branched polycarbonate resin in which a polyfunctional aromatic compound having three or more functional groups is copolymerized, and an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid copolymerized with a polycarbonate resin A polyester resin, a polyester carbonate resin, a copolymerized polycarbonate resin obtained by copolymerizing a bifunctional alcohol (including an alicyclic alcohol), a polyester carbonate resin obtained by copolymerizing the above bifunctional carboxylic acid and a bifunctional alcohol together, The above mixture may be used.

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

Examples of the aliphatic bifunctional carboxylic acid include aliphatic bifunctional carboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid , Straight-chain saturated aliphatic dicarboxylic acids such as icosanic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

Examples of the bifunctional alcohols include alicyclic diols such as cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

The weight average molecular weight of the polycarbonate resin contained in the base layer and the coating layer may be 1,000 g / mol to 300,000 g / mol, or 10,000 g / mol to 150,000 g / mol.

The process for synthesizing the polycarbonate is not particularly limited, but 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-phase ester exchange method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Examples of the divalent phenol are not particularly limited, but typical examples of the divalent phenol include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl Bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy- Butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, (4-hydroxyphenyl) pentane, 4,4'- (p-phenylenediisopropylidene) diphenol, 4,4 '- (m- Propylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4- isopropylcyclohexane, bis (4-hydroxyphenyl) Bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis Bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) -Hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene or 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

Examples of the carbonate precursor include, but are not limited to, a carbonyl halide, a carbonic acid diester or a haloformate, and preferably a phthalocyanine, a diphenyl carbonate or a dihaloformate of a dihydric phenol .

Specifically, for example, the reaction by the interfacial polymerization method may be carried out in the presence of an acid binder and an organic solvent in the reaction of bifunctional phenol and phosgene. 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 may be 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- Can be used. Examples of the monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol. The above monofunctional phenols are effective when it is required to improve the fluidity and hydrolysis resistance. The reaction temperature by the interfacial polymerization method is preferably 0 to 40 DEG C, the reaction time is 5 minutes to 5 hours, and the pH during the reaction is preferably 10 or more.

Examples of the reaction by the above-mentioned melt ester exchange method include a method in which a dihydric phenol and a carbonic acid diester are mixed in the presence of an inert gas in the transesterification reaction of a dihydric phenol and a carbonic acid diester, Lt; 0 &gt; C. The degree of decompression is changed stepwise, and finally, the pressure is reduced to 133 Pa or less, so that the generated phenols can be removed from the system. The reaction time is about 1 hour to 4 hours.

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 .

In addition, a polymerization catalyst may be used to accelerate the polymerization rate. 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 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 × 10 ^-9 to 1 × 10 ^-5 equivalent, more preferably 1 × 10 ^-8 to 5 × 10 ^{- 6} eq. It can be used as a range.

In the polymerization reaction, in order to reduce the phenolic end group, after the end or the end of the polymerization reaction, for example, 2-chlorophenylphenylcarbonate, 2-methoxycarbonylphenylphenylcarbonate and 2-ethoxycarbonylphenylphenyl A compound such as carbonate can be added.

In the 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, or 0.01 to 300 ppm, or 0.01 to 100 ppm. Examples of the deflocculating agent include a phosphonium salt such as dodecylbenzenesulfonic acid tetrabutylphosphonium salt and the like, and an ammonium salt such as tetraethylammonium dodecylbenzylsulfate.

The coating layer and the substrate layer may each contain 0.01 to 15 parts by weight, or 0.05 to 10 parts by weight, or 0.1 to 5 parts by weight of the ultraviolet absorber, based on 100 parts by weight of the polycarbonate resin. Thus, the weather resistance of the multilayer polycarbonate sheet can be improved without causing bleeding of the ultraviolet absorber on the surface of the multilayer polycarbonate sheet and deterioration of the mechanical properties.

The ultraviolet absorbent refers to a component that blocks ultraviolet energy or selectively absorbs ultraviolet energy to emit other types of energy that are not harmful to the polymer, or inhibits the photoreaction of the polymer, particularly the initiation of photodecomposition.

The ultraviolet absorber contained in the base layer and the coating layer may be selected from the group consisting of 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (3-tert- butyl- (2-hydroxy-3,5-bis (?,? - dimethylbenzyl) phenyl] - Benzene triazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3- Bis (1-methyl-1-phenylethyl) phenol, or a mixture of two or more thereof.

The coating layer and the substrate layer 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] [ Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], N, N'- Aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidylamino) -6- Triazine condensate, dibutylamine-1,3,5-triazine-N, N'-bis (2,2,6,6) -tetramethyl-4-piperidyl-1,6-hexamethylenediamine And a polycondensation product of N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine or a mixture of two or more thereof, preferably bis (2,2,6,6,6) -Tetramethyl-4-piperidyl) sebacate or bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

The hindered amine light stabilizer may be used in an amount of 0.001 part by weight to 1 part by weight, or 0.005 part by weight to 0.5 part by weight, or 0.01 part by weight to 0.2 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 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.

On the other hand, the coating layer and the substrate layer may further include a release agent to increase the productivity during 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 ester or all ester of monohydric or polyhydric alcohol and saturated fatty acid 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, Ethylhexyl stearate, ethylene glycol distearate, or a mixture of two or more thereof, preferably, stearic acid monoglyceride, stearic acid monoglyceride, stearic acid monoglyceride, stearic acid monoglyceride, , Stearic acid triglyceride, penta Erythritol tetrastearate, behen sambearyl, 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 to 2 parts by weight, or 0.001 to 1 part by weight, or 0.01 to 0.5 parts by weight based on 100 parts by weight of the polycarbonate resin.

The addition timing and addition method of the releasing agent are not particularly limited. For example, when the polycarbonate resin is prepared by transesterification, at the end of the polymerization reaction; A state in which the polycarbonate resin is melted during the kneading of the polycarbonate resin and another compounding agent regardless of the polymerization method; Or an extruder or the like to blend with a polycarbonate resin in a solid state such as pellets or powder; And the like. Examples of the addition method include a method of directly kneading or kneading the release agent with a polycarbonate resin; A method of adding a small amount of polycarbonate resin or other resin as a high-concentration master batch made by using the above releasing agent; Etc. may be used.

On the other hand, the coating layer and the substrate layer may further include an epoxy compound to further improve the hydrolysis resistance.

Specific examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ' , 4'-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) butyl-3', 4'-epoxycyclohexylcarboxylate, Hexyl ethylene oxide, 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, Epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxidarate, epoxidized polybutadiene, 3, 5-epoxycyclohexyl adipate, bis-epoxy dicyclopentadienyl ether, bis- Dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t- -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-3 ', 4 Epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,5-epoxy anhydride tetrahydro 3-t-butyl-4,5-epoxy anhydride tetrahydrophthalic acid, diethyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di- Butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, and the like, and preferably bisphenol A diglycidyl ether can be used.

The epoxy compound may be used in an amount of 0.0001 to 5 parts by weight, or 0.001 to 1 part by weight, or 0.005 to 0.5 parts by weight based on 100 parts by weight of the polycarbonate resin. With the use of the epoxy compound in the above range, the hydrolysis resistance can be improved without causing deterioration of the mechanical properties of the bleeding of the epoxy compound onto the surface of the multilayer polycarbonate sheet and various molded articles.

The coating layer and the substrate layer may further include a heat stabilizer to prevent the deterioration of the molecular weight and the hue of the color. 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, or 0.0005 parts by weight to 0.5 parts by weight, or 0.001 parts by weight to 0.2 parts 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.

Further, the coating layer and the substrate layer may further comprise an antioxidant. Specific examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, 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- -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 parts by weight to 1 part by weight, or 0.0005 parts by weight to 0.5 parts by weight, or 0.001 parts by weight to 0.2 parts by weight based on 100 parts by weight of the polycarbonate resin.

On the other hand, the coating layer and the substrate layer 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, it may further include at least one other polymer resin selected from the group consisting of polyester resin, polyether, polyamide, polyolefin, and polymethyl methacrylate. The other polymer resin may be added in an amount of 1 to 30 parts by weight, or 3 to 20 parts by weight, or 5 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin.

The multilayer polycarbonate sheet is preferably transparent depending on the properties required in the field of use. The transparency of the multilayer polycarbonate sheet can be evaluated by the total light transmittance in the visible light range of the multilayer polycarbonate sheet, and it is preferable that the transparency of the multilayer polycarbonate sheet is high.

Specifically, the multilayer polycarbonate sheet has a transmittance at a wavelength of 800 nm to 1,300 nm (near-infrared ray) at a thickness of 3.1 mm and a transmittance of 85% or less, or 20% to 85% at a wavelength of 400 nm to 750 nm (visible light) Lt; / RTI &gt; The transmittance was measured using a multilayer polycarbonate sheet composed of a 50 mu m thick coating layer bonded to both sides of a substrate layer having a thickness of 3 mm.

The multilayer polycarbonate sheet is useful for various uses such as a window pane for a vehicle, a lamp for a vehicle, and a window pane for a building material.

Also, the multilayer polycarbonate sheet may have a yellowing index change amount of 1.6 or less, or 1.0 to 1.55 according to the following formula (1).

[Equation 1]

Yellowing index change (DELTA YI) = yellowing index of multi-layer polycarbonate sheet subjected to weathering test for 2000 hours by SAE J1960 - yellowing index of initial multilayer polycarbonate sheet

In the above Equation 1, the yellow index was measured by ASTM D1925.

As the multilayer polycarbonate sheet has a yellowing index change amount in the above-mentioned range, the multilayer polycarbonate sheet can be minimized in yellowing due to ultraviolet rays even when exposed to an ultraviolet ray environment for a long time.

The coating layer of the multilayer polycarbonate sheet may further include an organic metal complex including a polymer binder resin and metal particles. Since the coating layer includes the organic metal complex including the polymer binder resin and the metal particles, it is possible to greatly increase the rejection ratio for the light 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.

And may have a weight average molecular weight of, for example, 50,000 to 500,000, or 100,000 to 300,000, or 0.870 g / cm3 to 0.970 g / cm3, or 0.9 g / cm &lt; 3 &gt; to 0.95 g / cm &lt; 3 &gt;.

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.

According to the present invention, it is possible to provide a multilayer polycarbonate sheet having high light transmittance in the visible light region, excellent light shielding property in the infrared and near infrared region, and high heat resistance, weather resistance and scratch resistance.

Fig. 1 schematically shows the structure of the multilayer sheet of the embodiment.
2 shows the transmittance according to the wavelengths of the examples and comparative examples measured in Experimental Example 1. FIG.
FIG. 3 is a graph showing changes in yellowing index according to time in Examples and Comparative Examples measured in Experimental Example 2. FIG.
4 shows SEM photographs of the composite metal oxides used in Examples 1 and 2, respectively.
5 is a SEM photograph of the organometallic complex used in Example 3. Fig.

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.

< Production Example 1 : Production 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 pressure was slowly lowered to 0 torr at 760 torr, and the condensation reaction proceeded to synthesize a polycarbonate resin.

< Example  1 to 3: Preparation of multilayer polycarbonate sheet>

(1) Production of Base Layer Sheet

The polycarbonate resin and the ultraviolet absorber (2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol manufactured by BASF) The mixture was blended using a blender according to the contents, and then melt-kneaded and extruded at a discharge rate of 15 kg / h, a screw rotation speed of 200 rpm, and a temperature of 290 ° C by using a vented twin-screw extruder to produce pellets.

The base layer resin pellets were supplied to an extruder having a screw diameter of 90 mm, melted at 280 캜, and extruded through a T-die to prepare a base layer sheet.

(2) Production of coated layer sheet

Polycarbonate resin, ultraviolet absorber, composite metal oxide (SnSb ₂ Cs ₂ WO ₉ ) and organometallic complex were mixed using the blender according to the contents shown in the following Table 1, and then extruded at a discharge rate of 15 kg / h, a screw rotation speed of 200 rpm, and a temperature of 290 ° C to produce pellets.

The coating resin pellets were supplied to an extruder having a screw diameter of 45 mm and melted at 280 캜 and extruded through a T-die to prepare a coated layer sheet.

(3) Production of multilayer polycarbonate sheet

The substrate layer sheet and the coated layer sheet were bonded together by a roll to produce a multilayer polycarbonate sheet having a covering layer formed on both surfaces of the base layer. At this time, the thickness of the base layer was 3 mm and the thickness of the coating layer was 50 m.

< Comparative Example  1: Preparation of multilayer polycarbonate sheet &gt;

As shown in the following Table 1, a multilayer polycarbonate sheet was prepared in the same manner as in Example 1 except that the content of the composite metal oxide used in the reaction was different.

< Comparative Example  2 to 4: Preparation of single-layer polycarbonate sheet>

The polycarbonate resin and the ultraviolet absorber of the above production example were mixed using a blender according to the contents shown in the following Table 1 and then melted at a discharge rate of 15 kg / h, a screw rotation speed of 200 rpm, and a temperature of 290 캜 using a vent type twin- Kneaded and extruded to prepare pellets.

The resin pellets were supplied to an extruder having a screw diameter of 90 mm and melted at 280 캜 and extruded through a T-die to prepare a single-layer polycarbonate sheet.

< Experimental Example  : Example  And In the comparative example  Measurement of physical properties of the obtained polycarbonate sheet>

The properties of the polycarbonate sheet obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.

1. Transmittance (%)

1-1. Near Infrared Transmittance (%)

The transmittance of the polycarbonate sheet obtained in Examples 1 to 3 and Comparative Examples 1 to 4 was measured at 800 to 1300 nm band using a UV-3600 model manufactured by Shimadzu Co., and the result is shown in Fig.

1-2. Visible light transmittance (%)

The transmittance of the polycarbonate sheet obtained in Examples 1 to 3 and Comparative Examples 1 to 4 was measured at 400 to 750 nm band using a UV-3600 model manufactured by Shimadzu Co., and the result is shown in FIG.

2. Yellowness Index (YI) The amount of change (YI)

The first yellowing index of the polycarbonate sheet obtained in Examples 1 to 3 and Comparative Examples 1 to 4 was measured according to the ASTM D1925 standard using a Coloreye 7000A model of X-rite.

The polycarbonate sheet obtained in Examples 1 to 3 and Comparative Examples 1 to 4 was subjected to a weather resistance test under the SAE J1960 standard for a predetermined time using a Ci 4000 model of Atlas Co., Were measured.

The amount of change in the yellowing index (the second yellowing index-the first yellowing index) with the time when the above weathering test was performed is shown in FIG.

The sheet compositions of Examples and Comparative Examples and the results of Experimental Examples are shown in Table 1 below.

Sheet compositions of Examples and Comparative Examples and results of Experimental Examples division unit Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 The substrate layer Polycarbonate Weight portion 100 100 100 100 100 100 11 Ultraviolet absorber 0.1 0.1 0.1 0.1 0.125 1.1 0.1 Coating layer Polycarbonate 100 100 100 100 - - - Ultraviolet absorber 1.5 1.5 1.5 1.5 - - - Composite metal oxide 0.02 0.05 0.02 - - - - Organometallic complex
(Al / Olefin) - - 0.003 - - - - NIR transmittance
(800 nm to 1,300 nm) % 84.29 77.71 73.25 88.81 89.35 89.42 90.72 Visible light transmittance
(400 nm to 750 nm) 82.77 84.89 76.57 85.85 88.23 85.83 88.54 Yellowing index change amount
(2,000 hours of weathering test) 1.52 1.27 1.18 1.64 6.51 1.73 7.21

- 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. 5 )

As shown in Table 1, Comparative Example 1 has a multi-layer structure of a coating layer and a substrate layer, but unlike the examples, the coating layer does not contain a composite metal oxide, and the near infrared ray transmittance is as high as 88.81% In Examples 1 and 2, a composite metal oxide was contained in the coating layer, and the near infrared ray transmittance was measured as low as 84.29% and 77.71%, respectively. In particular, in the case of Example 3 including the organometallic complex in addition to the composite metal oxide in the coating layer, the near infrared ray transmittance was lowered to 73.25%, and the light shielding property in the near infrared region was remarkably improved.

The visible light transmittance was measured to be 82.77% for Example 1, 84.89% for Example 2, and 76.57% for Example 3, which was high enough to be equivalent to 85.85% of visible light transmittance of Comparative Example 1, It can be confirmed that the polycarbonate sheet exhibits high light transmittance in the visible light region and excellent light shielding property in the near infrared region.

On the other hand, in the case of Comparative Examples 2 to 4, it was confirmed that the near infrared ray transmittance was as high as 89% or more because of the single layer structure not including the composite metal oxide, and the light shielding property was reduced in the infrared and near infrared ray regions.

In addition, the amount of yellowing index change was measured to be lower than that of Comparative Example 1 to Comparative Example 4, which was 1.52 in Example 1, 1.27 in Example 2, and 1.18 in Example 3. From these results, it can be seen that the multilayer polycarbonate sheet of the above example includes the coating layer containing the composite metal oxide or the organic metal complex and the substrate layer, and Comparative Examples 2 to 4 comprising only the base layer without the coating layer and Comparative Examples 2 to 4 containing only the ultraviolet absorbing agent 1, it can be confirmed that it has excellent weather resistance.

1: substrate layer
2:

Claims (21)

A substrate layer including a polycarbonate resin and an ultraviolet absorber; And
Wherein at least one member selected from the group consisting of polycarbonate resin, ultraviolet absorber and Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb and Cs And a coating layer containing a composite metal oxide including a metal and tungsten,
Wherein the composite metal oxide comprises a compound of formula (1): < EMI ID = 6.1 &gt;
[Chemical Formula 1]
M1 _x1 M2 _x2 M3 _x3 W _y O _z
M 1, M 2, and M 3 may be the same or different from each other and are Bi, Cu, Cd, Ca, Co, Mn, Cr, Mg, Fe, Mo, Sn, Sb,
1.0 &lt; (x1 + x2 + x3) / y? 10.0,
3.0 &lt; z / y &amp;le; 30.0.
The method according to claim 1,
Wherein the coating layer comprises 0.00001 to 1 part by weight of the composite metal oxide per 100 parts by weight of the polycarbonate resin.
delete The method according to claim 1,
In Formula 1,
0.1 <x1? 10.0, 0.1 <x2? 10.0, 0.1 <x3? 10.0, and 7.0? Z? 11.0.
The method according to claim 1,
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,
And at least one of the base layer and the covering layer.
The method according to claim 1,
Wherein the ratio of the thickness of the base layer to the thickness of the coating layer is 5: 1 to 100: 1.
The method according to claim 1,
Wherein the base layer and the polycarbonate resin contained in the coating layer have a weight average molecular weight of 1,000 g / mol to 300,000 g / mol.
The method according to claim 1,
The ultraviolet absorber contained in the base layer and the coating layer may be selected from the group consisting of 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (3-tert- butyl- (2-hydroxy-3,5-bis (?,? - dimethylbenzyl) phenyl] - Benzene triazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis And at least one selected from the group consisting of 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol.
The method according to claim 1,
Wherein the coating layer and the substrate layer each comprise 0.01 to 15 parts by weight of the ultraviolet absorbing agent per 100 parts by weight of the polycarbonate resin.
The method according to claim 1,
Wherein the coating layer and the base layer each further comprise 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 coating layer and the base layer each further comprise at least one other polymer resin selected from the group consisting of a polyester resin, polyether, polyamide, polyolefin, and polymethyl methacrylate.
The method according to claim 1,
Wherein the coating layer further comprises an organometallic complex including a polymeric binder resin and metal particles.
15. The method of claim 14,
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.
15. The method of claim 14,
Wherein the metal particles contained in the organometallic complex include aluminum or aluminum oxide.
15. The method of claim 14,
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.
15. The method of claim 14,
Wherein the metal particles have a longest diameter of 1 占 퐉 to 100 占 퐉.
The method according to claim 1,
A multilayer polycarbonate sheet having an infrared and near infrared transmittance of less than 85% at a thickness of 3.1 mm.
The method according to claim 1,
A multilayer polycarbonate sheet having a yellowing index change amount (DELTA YI) according to the following formula (1) is 1.6 or less:
[Equation 1]
Yellowing index change (DELTA YI) = yellowing index of multi-layer polycarbonate sheet subjected to weathering test for 2000 hours by SAE J1960 - yellowing index of initial multilayer polycarbonate sheet
The method according to claim 1,
A multilayer polycarbonate sheet used as a vehicle window member or a construction window member.

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