Near-infrared ray shielding film, a method thereof, and a composition thereof

Abstract

A method of manufacturing a near-infrared ray shielding film is disclosed. The method comprises: providing a raw material of PET; providing tungsten oxides-containing nanoparticles; blending the raw material of PET and the tungsten oxides-containing nanoparticles to obtain a polyester mixture with 80-99.99 wt % of the raw material of PET and 0.01-20 wt % of the tungsten oxides-containing nanoparticles; rolling the polyester mixture to obtain a polyester sheet; and biaxially-orientating the polyester sheet with a orientating rate of 1-100 meters per minute at 60-300 C.

Claims

1. A method of manufacturing a near-infrared ray shielding film comprising: drying a raw material of PET at 110 C. for 12 hours until the raw material of PET has a water content below 30 ppm; vacuum drying Cs.sub.0.33WO.sub.3 nanoparticles at 80 C. for 12 hours, wherein each of the Cs.sub.0.33WO.sub.3 nanoparticles has a size of 68 nm; blending the dried raw material of PET and the dried Cs.sub.0.33WO.sub.3 nanoparticles at 240-330 C. by a twin screw extruder with a screw speed between 300 and 600 rpm to obtain a polyester mixture with 99.14 wt % of the raw material of PET and 0.86 wt % of the dried Cs.sub.0.33WO.sub.3 nanoparticles; extruding the polyester mixture at 50-60 C. to obtain a polyester sheet; and biaxially orientating the polyester sheet with an orientating rate of 30 meters per minute at 160-165 C.

2. The method of manufacturing a near-infrared ray shielding film as claimed in claim 1, wherein an additive selected from a group consisting of UV protective agents, light stabilizers, durability-improving agents, anti-hydrolysis-improving agents, heat resistant agents, lubricants and crystallinity-improving agents is further added to the dried raw material of PET before blending the dried raw material of PET and the dried Cs.sub.0.33WO.sub.3 nanoparticles.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The present invention will become more fully understood from the detailed description given hereinafter and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:

(2) FIG. 1 is an outer appearance view of a near-infrared ray shielding film according to the invention.

(3) FIG. 2 is a cross-sectional, enlarged view of the near-infrared ray shielding film according to the invention.

(4) In the various figures of the drawings, the same numerals designate the same or similar parts. Furthermore, when the term first, second, third, fourth, inner, outer, top, bottom and similar terms are used hereinafter, it should be understood that these terms refer only to the structure shown in the drawings as it would appear to a person viewing the drawings, and are utilized only to facilitate describing the invention.

DETAILED DESCRIPTION OF THE INVENTION

(5) The composition for shielding near-infrared ray according to the invention comprises 80-99.9 wt % of PET (poly ethylene terephthalate) and 0.01-20 wt % of a tungsten oxides-containing nanoparticle. The tungsten oxides-containing nanoparticle is selected from a group consisting of a nanoparticle of tungsten oxides and a nanoparticle of tungsten bronzes.

(6) The tungsten oxides-containing nanoparticle are particles between 1 and 800 nm in size, and preferably, between 10 and 195 nm. The nanoparticle of tungsten oxides is represented by a formula WO.sub.x, wherein W represents tungsten, O represents oxygen, and x is a number satisfying requirements 2.2x3. Moreover, the nanoparticle of tungsten bronzes is represented by a formula A.sub.yWO.sub.z, wherein A represents at least one chemical elements selected from main group elements, W represents tungsten, O represents oxygen, and y and z are numbers satisfying requirements 0.01y1 and 2.2z3, respectively. Preferably, A represents at least one chemical elements selected form lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, gallium, carbon, silicon, tin, antimony, fluorine, chlorine, bromine or iodine. The nanoparticle of tungsten bronzes can be represented by a formula selected form Cs.sub.0.33WO.sub.3, K.sub.0.33WO.sub.3, K.sub.0.55WO.sub.3, Na.sub.0.5WO.sub.3 or Ba.sub.0.33WO.sub.3. In the embodiment, the nanoparticle of tungsten oxides and the nanoparticle of tungsten bronzes are represented by formulas WO.sub.2.72 and Cs.sub.0.33WO.sub.3, respectively.

(7) The composition for shielding near-infrared ray comprises the tungsten oxides-containing nanoparticle poses effect on shielding near-infrared ray; thus, the composition for shielding near-infrared ray can be processed to form a near-infrared ray shielding film which can be broadly used to paste on the windows. Referring to FIGS. 1 and 2, the near-infrared ray shielding film comprises a PET film 1 and a plurality of tungsten oxides-containing nanoparticles 2. The plurality of tungsten oxides-containing nanoparticles 2 are spread and mounted in the PET film 1. The near-infrared ray shielding film comprises 80-99.99 wt % of PET and 0.01-20 wt % of the tungsten oxides-containing nanoparticle 2. The near-infrared ray shielding film has a thickness d, and preferably, the thickness d is between 1 to 1000 m.

(8) In detail, as mentioned above, the tungsten oxides-containing nanoparticle can be selected from a group consisting of a nanoparticle of tungsten oxides and a nanoparticle of tungsten bronzes. The tungsten oxides-containing nanoparticle are particles between 1 and 800 nm in size, and preferably, between 10 and 195 nm. The nanoparticle of tungsten oxides is represented by a formula WO.sub.x, wherein W represents tungsten, O represents oxygen, and x is a number satisfying requirements 2.2x3. Moreover, the nanoparticle of tungsten bronzes is represented by a formula A.sub.yWO.sub.z, wherein A represents at least one chemical elements selected from main group elements, W represents tungsten, O represents oxygen, and y and z are numbers satisfying requirements 0.01y1 and 2.2z3, respectively. Preferably, A represents at least one chemical elements selected form lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, gallium, carbon, silicon, tin, antimony, fluorine, chlorine, bromine or iodine. The nanoparticle of tungsten bronzes can be represented by a formula selected form Cs.sub.0.33WO.sub.3, K.sub.0.33WO.sub.3, K.sub.0.55WO.sub.3, Na.sub.0.5WO.sub.3 or Ba.sub.0.33WO.sub.3. In the embodiment, the nanoparticle of tungsten oxides and the nanoparticle of tungsten bronzes are represented by formulas WO.sub.2.72 and Cs.sub.0.33WO.sub.3, respectively.

(9) A method for manufacturing a near-infrared ray shielding film as mentioned before is also disclosed in the invention. The method comprises: providing a raw material of PET; providing a tungsten oxides-containing nanoparticle; blending the raw material of PET and the tungsten oxides-containing nanoparticles at 180-360 C. to obtain a polyester mixture with 80-99.99 wt % of the raw material of PET and 0.01-20 wt % of the tungsten oxides-containing nanoparticles; extrusing (extrusion molding) or compression molding the polyester mixture to obtain a polyester sheet; and uniaxially- or biaxially-orientating the polyester sheet with a orientating rate of 1-100 meters per minute at 60-300 C.

(10) In detail, the raw material of PET includes PET. Preferably, before blending the raw material of PET and the tungsten oxides-containing nanoparticles, an additive selected from a group consisting of UV protective agents, light stabilizers, durability-improving agents, anti-hydrolysis-improving agents, heat resistant agents, lubricants and crystallinity-improving agents is further added to the raw material of PET. The additive can be benzophenone type (2-hydroxy-4-n-octyloxy-benzophenone, etc.), benzotriazole type (5-Methyl-1H-benzotriazole, etc.), triazine type (TRIMETHOXY-S-TRIAZINE, etc.), oxanilide type, hinder amine light stabilizer (Bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, etc.), wax, salts, esters, amides of stearic acid, lead salts, organotin compounds, 2,6-di-tert-butyl-4-methylphenol. The tungsten oxides-containing nanoparticle is the same as mentioned before.

(11) Then, the raw material of PET and the tungsten oxides-containing nanoparticle are blended at 180-360 C. to obtain the transparent polyester mixture. Preferably, the raw material of PET and the tungsten oxides-containing nanoparticle are blended at 200-340 C. In particular, the raw material of PET and the tungsten oxides-containing nanoparticle are blended by a single screw extruder or a twin screw extruder. Alternatively, the raw material of PET and the tungsten oxides-containing nanoparticle are blended by a Brabender. If the raw material of PET and the tungsten oxides-containing nanoparticle are blended by the twin screw extruder, the screw rotating speed is 50-950 rpm. If the raw material of PET and the tungsten oxides-containing nanoparticle are blended by the Brabender, the rotating speed is 10-100 rpm.

(12) In the embodiment, the raw material of PET and the tungsten oxides-containing nanoparticle are blended by the twin screw extruder at 240-330 C. with the screw rotating speed of 100-900 rpm. Because of the high shearing force of the twin screw extruder, the raw material of PET and the tungsten oxides-containing nanoparticle can be kneaded, plasticized, sheared and homogenized, and therefore the raw material of PET and the tungsten oxides-containing nanoparticle can be uniformly blended.

(13) The polyester sheet is further obtained by extrusing (extrusion molding) or compression molding the polyester mixture. The polyester mixture can be rolled by a casting drum, and therefore the polyester sheet with uniform thickness can be obtained. The polyester mixture can be rolled at 30-180 C., preferably at 50-150 C. In the embodiment, the polyester mixture extruded form the twin screw extruder can be rolled at 30-100 C. by the casting drum to obtain the polyester sheet. Alternatively, a strip-like product extruded from the twin screw extruder can be further cut to form granules. The formed granules can be compression molded at 180-350 C. to obtain the polyester sheet.

(14) The temperature of the casting drum used in the embodiment is preferably lower than the glass transform temperature Tg of the raw material of PET, ensuring the polyester mixture can be quickly cooled down form melted status and thereby controlling the crystallization status of the raw material of PET of the polyester mixture. The higher the crystallization status is, the haze of the polyester mixture increases and the easier the obtained polyester sheet breaks.

(15) The polyester sheet is uniaxially- or biaxially-orientated to obtain the near-infrared ray shielding film. The polyester sheet can be orientated along an orientating direction and obtained the near-infrared ray shielding film with an improved mechanical strength in the orientated direction. In detail, the polyester sheet is uniaxially- or biaxially-orientated at 60-300 C., and preferably at 80-280 C. with an orientating rate of 1-100 meters per minute. Besides, the biaxially-orientation can be continuous two-step extrusion or single-step synchronous extrusion. In the continuous two-step extrusion, the polyester sheet is vertically compression molded by a heated drum, followed by horizontally extrusion in an oven. In the embodiment, the biaxially-orientation is single-step synchronous extrusion using Bruchner KARO IV with a heated circulating motor with a rotating speed of 800-3000 rpm. By using the heated circulating motor, the polyester sheet is biaxially-orientation with the orientating rate of 1-100 meters per minute at 80-240 C. with the orientating fold between 1 and 9, to obtain the near-infrared ray shielding film with a preferable thickness of 1-1000 m.

(16) Preferably, the near-infrared ray shielding film can be heat treated to release the remained internal stress after rolling and biaxially-orientation, such as decreasing the thermal shrinkage rate of the near-infrared ray shielding film. The heat treatment is performed at 60-300 C., and preferably at 80-280 C. for 1-120 minutes. In the embodiment, the heat treatment is performed at 100-240 C. for 1-60 minutes.

(17) Preferably, before blending, the raw material of PET can be dried to remove water inside, preventing the raw material of PET from degradation in the manufacturing process. The raw material of PET can be dried until the water content below 30 ppm by circulating airflow drying method, heating drying method or vacuum drying method. For example, in the circulating airflow drying method, the raw material of PET is kept at 110-160 C. for 60 minutes, followed by keeping at 170-190 C. for 3-12 hours. Moreover, in the vacuum drying method, the raw material of PET is kept at 120-150 C. for 6-12 hours. Furthermore, the tungsten oxides-containing nanoparticle also can be dried before blending. By the drying process, the quality of the obtained near-infrared ray shielding film can be improved, preventing from the hazing problem due to water vapor accumulation.

(18) That is, the near-infrared ray shielding film can be obtained via low-cost blending, extruding and rolling devices, thereby decreasing the production cost of the near-infrared ray shielding film. Besides, the tungsten oxides-containing nanoparticles with effect on shielding near-infrared ray uniformly separates inside, thereby preventing from the poor binding at the boundary and further extending the durability of the near-infrared ray shielding film. Moreover, the near-infrared ray shielding film with the tungsten oxides-containing nanoparticles manufactured by a proper method poses a better effect on shielding near-infrared ray.

(19) In order to evaluate the near-infrared ray shielding film of the invention poses the better effect on shielding near-infrared ray, and to demonstrate the near-infrared ray shielding film poses the best effect on shielding near-infrared ray, the near-infrared ray shielding films of groups A1 to A7 obtained using different parameters including temperature and time of drying the raw material of PET, composition and the particle size of the tungsten oxides-containing nanoparticle, weight of the raw material of PET per square meter of the final product, rotating speed of the screw, the depth of the polyester sheet, temperature of rolling, temperature of compression molding, temperature, orientating speed, orientating fold of biaxially-orientating, temperature of heat treatment, depth of the near-infrared ray shielding film. The near-infrared ray shielding film without the tungsten oxides-containing nanoparticle named group A0 is used as a control.

(20) Before blending, the tungsten oxides-containing nanoparticles are vacuum drying at 80 C. for 12 hours. The blending is performed at 240-330 C. The rotating speed of the heated circulating motor of Bruchner KARO IV is set at 1700 rpm. The detailed parameters are listed in TABLE 1. The weight of the tungsten oxides-containing nanoparticle per square meter of the final product is calculated as following: weight of the weight of the tungsten oxides-containing nanoparticle (gram) divided by the area of the near-infrared ray shielding film (m.sup.2).

(21) TABLE-US-00001 TABLE 1 Group Group Group Group Group Group Group Group A0 A1 A2 A3 A4 A5 A6 A7 PET 110 110 110 110 80 80 80 80 drying temperature ( C.) PET 12 12 12 12 12 12 12 12 drying time (hour) Composition X Cs.sub.0.33WO.sub.3 Cs.sub.0.33WO.sub.3 WO.sub.2.72 Cs.sub.0.33WO.sub.3 Cs.sub.0.33WO.sub.3 Cs.sub.0.33WO.sub.3 WO.sub.2.72 of the tungsten oxides- containing nanoparticle Particle X 68 68 72 68 68 68 68 size of the tungsten oxides- containing nanoparticle (nm) PET 0 99.14 99.14 99.14 98.92 82.14 99.96 99.91 wt % Tungsten 0 0.86 0.86 0.86 1.08 17.86 0.04 0.09 oxides- containing nanoparticle (wt %) Weight 0 0.6 0.6 0.6 1.5 3 0.3 0.6 of the tungsten oxides- containing nanoparticle per square meter of the final product (g/m.sup.2) Rotating 300-600 300-600 300-600 300-600 300-600 100-300 600-900 600-900 speed of the screw (rpm) Thickness 450 50 450 450 400 90 2000 2000 of the polyester sheet (m) Temperature 50-60 X 50-60 50-60 60-70 50-60 270-280 270-280 of rolling of compression molding ( C.) Temperature 160-165 X 160-165 160-165 170-195 160-165 190-215 190-215 of biaxially- orientating ( C.) Orientating 30 X 30 30 15 15 30 30 speed of biaxially- orientating (m/min) Orientating 9 X 9 9 4 9 4 4 fold of biaxially- orientating Temperature 160-190 160-190 160-190 160-190 170-200 160-190 170-200 170-200 of heat treatment ( C.) Thickness 50 50 50 50 100 10 500 500 of the near-infrared ray shielding film (m)

(22) Referring to TABLE 1, the near-infrared ray shielding film of group A0 is made without the nanoparticles containing tungsten oxide. The only different parameter between groups A1 and A2 is the near-infrared ray shielding film of group is manufactured without biaxially-orientating, therefore, the thickness of the polyester sheet of group A1 is the same as the thickness of the near-infrared ray shielding film. Moreover, in groups A6 and A7, the rotation speed of the screw much higher than the others results in the granules-like polyester mixture, therefore, the high-temperature compression molding is used to form the polyester sheet.

(23) The optical property of the near-infrared ray shielding film of groups A0 to A7 is shown in the following TABLE 2. The transmittance of visible light and sunlight are measured according to the standard ISO9050.

(24) TABLE-US-00002 TABLE 2 Weight of the tungsten oxides-containing nanoparticle Thickness per square Composition of the meter of the of the near-infrared final tungsten ray Solar product oxides-containing shielding Light direct Group (g/m.sup.2) nanoparticle film transmittance transmittance A0 X X 50 89.1 88.9 A1 0.6 Cs.sub.0.33WO.sub.3 50 77.6 45.5 A2 0.6 Cs.sub.0.33WO.sub.3 50 78.2 45.7 A3 0.6 WO.sub.2.72 50 74.8 59.1 A4 1.5 Cs.sub.0.33WO.sub.3 100 65.1 27.3 A5 3 Cs.sub.0.33WO.sub.3 10 45.8 13.7 A6 0.3 Cs.sub.0.33WO.sub.3 500 85.5 55.2 A7 0.6 WO.sub.2.72 500 73.7 58.8

(25) Referring to TABLE 2, compared to group A0, all of groups A1 to A7 shows apparently decreased level of the transmittance of visible light and sunlight. Moreover, the decreased level of the solar direct transmittance is higher than the decreased level of the transmittance of visible light. It is worthy to note that sunlight approximately includes 52% of infrared light, 43% of visible light and 5% of ultraviolet light. Therefore, it is understood that the higher decreased level of the solar direct transmittance than the decreased level of the transmittance of visible light indicates part of the decreased level of sunlight is due to the decreased level of the transmittance of infrared light. As a result, the addition of the tungsten oxides-containing nanoparticles poses the improved effect on shielding near-infrared ray of the near-infrared ray shielding film of groups A1 to A7. Moreover, the near-infrared ray shielding films of groups A2 and A3 with the transmittance of visible light higher than 70% and the solar direct transmittance lower than 50% pose the best effect on shielding near-infrared ray.

(26) Moreover, the only different parameter between groups A2 and A3 is the composition and the particle size of the tungsten oxides-containing nanoparticle. That is, the tungsten oxides-containing nanoparticle used in group A2 is represented by the formula Cs.sub.0.33WO.sub.3 with the particle size of 68 nm, and the tungsten oxides-containing nanoparticle used in group A3 is represented by the formula WO.sub.2.72 with the particle size of 72 nm. Therefore, according to the results shown in TABLE 2, on the circumstance of similar particle size, compared to the tungsten oxides-containing nanoparticle represented by the formula WO.sub.2.72, the tungsten oxides-containing nanoparticle represented by the formula Cs.sub.0.33WO.sub.3 shows a better effect on shielding near-infrared ray.

(27) Five of the near-infrared ray shielding films with size of 150 mm10 mm are roasted at 150 C. for 30 minutes, followed by measuring the final size of the roasted near-infrared ray shielding films. The thermal shrinkage rate shown in TABLE 3 is calculated by dividing the mean value of the size of the roasted near-infrared ray shielding films by the mean value of the size of the near-infrared ray shielding films.

(28) TABLE-US-00003 TABLE 3 Group Thermal shrinkage rate (%) A2 5 A3 1

(29) Referring to TABLE 3, the near-infrared ray shielding film of group A2 without biaxially-orientating has a higher thermal shrinkage rate. As mentioned before, the near-infrared ray shielding film can be used to attach on transparent base material (i.e. glass). Therefore, the higher thermal shrinkage rate may result in easily peeling off from the transparent base material.

(30) In conclusion, because of the addition of the tungsten oxides-containing nanoparticle with effect on shielding near-infrared ray, the composition for shielding near-infrared ray and the near-infrared ray shielding film of the invention pose the improved effect on shielding near-infrared ray, further improving the adiabatic property of the composition for shielding near-infrared ray and the near-infrared ray shielding film of the invention.

(31) Moreover, the near-infrared ray shielding film of the invention comprises the plurality of tungsten oxides-containing nanoparticles which spread and mounted in the PET film, preventing from the problem of poor binding at the boundary, and thereby improving the durability of the near-infrared ray shielding film.

(32) In addition, the near-infrared ray shielding film of the invention is made via low-cost blending, extruding and rolling devices, and therefore the production cost of the near-infrared ray shielding film can be decreased.

(33) Although the invention has been described in detail with reference to its presently preferable embodiment, it will be understood by one of ordinary skill in the art that various modifications can be made without departing from the spirit and the scope of the invention, as set forth in the appended claims.