Patent Grant
9950340
This application claims priority to Korean Patent Application No. 10-2014-0118611, filed on Sep. 5, 2014, and all the benefits accruing therefrom under 35 U.S.C. § 119, the contents of which in its entirety are herein incorporated by reference.
1. Field
The present disclosure relates to a transparent heat-insulating material including polymer capsules and a method for producing the same.
2. Description of the Related Art
Many attempts have been made to save cost required for cooling and heating of buildings, particularly glass-walled buildings constructed largely in recent years.
Energy consumption in glass-walled buildings reaches 24% of the total energy consumption, and heat loss through windows occupies 30% of the total energy consumption on average and at least 7% of the total energy loss. Since the heat transfer coefficient of a window is at least 5 times higher than that of the outer wall or roof of a building, such a window is a main cause of heat loss. Moreover, in summer, solar radiation transmits through a window, which is one of the causes of cooling load, resulting in 66% of cooling load. In winter, during indoor heating, heat escapes through a window, which is one of the causes of heating load, and heat loss through a window reaches for 92% of heating load.
Therefore, many attentions have been given to improvement in the heat-shielding performance of a building window system. As a solution therefor, according to the related art, there has been suggested a method for connecting an inner part of a frame and an outer part thereof to each other with a non-metallic heat-insulating material having low heat conductivity to accomplish interruption of heat flow. In addition, air caps have been used to prevent conduction of cold air from outside through a glass window.
Further, some efforts have been made to increase heat-insulating quality through a temperature difference by introducing inert filler gas, such as air, argon or krypton, directly to pair glass.
However, according to the observation by the present inventors, the use of air caps or direct introduction of inert filler gas according to the related art is problematic in that it is difficult to ensure related techniques, such as durability upon sealing of such filler gas, gas mixing processes or control of mixing ratio, and further in that complicated processes are required and cost-efficiency is low.
Meanwhile, according to the related art (Korean Patent Publication No. 0870908), a method for producing a film-like glass heat-insulating material is disclosed, and the method includes carrying out extrusion molding of a blend of a polyvinyl chloride resin, microsilica capsules and a plasticizing agent.
However, according to the observation by the present inventors, the method is problematic in that it is not possible to control a size of microsilica capsules that affect transparency and heat-insulating property of glass, and thus it is difficult to control the transparency and heat-insulating property. Moreover, the method involves complicated processes.
In one aspect, the present disclosure is directed to providing a transparent heat-insulating material and a method for producing the same wherein the transparent heat-insulating material may has an excellent heat-insulating property in such a manner that a transmission of radiative heat of solar radiation energy entering from outside is reduced and discharge or loss of heat when indoor heating is prevented, while showing high transparency as well.
In another aspect, the present disclosure is also directed to providing a transparent heat-insulating material and a method for producing the same wherein the transparent heat-insulating material may allow easy control of the size of capsules contained in the transparent heat-insulating material, and the method for producing the transparent heat-insulating material involves simple and easy processes and is suitable for mass production.
In yet another aspect, the present disclosure is also directed to providing a method for controlling transparency and heat-insulating property of a transparent heat-insulating material with ease.
In example embodiments, there is provided a transparent heat-insulating material including a transparent heat-insulating resin layer, wherein the transparent heat-insulating layer includes an optical resin; and polymer capsules.
In example embodiments, there is provided a method for producing a transparent heat-insulating material, including: preparing polymer capsules; and mixing the polymer capsules with an optical resin.
Example embodiments are described more fully hereinafter. The invention may, however, be embodied in many different forms and should not be construed as limited to the example embodiments set forth herein. Rather, these example embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the description, details of features and techniques may be omitted to more clearly disclose exemplary embodiments.
As used herein, the singular forms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. Furthermore, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item. The terms “first,” “second,” and the like do not imply any particular order, but are included to identify individual elements. Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguished one element from another. It will be further understood that the terms “comprises” and/or “comprising”, or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. All methods described herein can be performed in a suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”), is intended merely to better illustrate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention as used herein.
Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings.
As used herein, ‘transparent heat-insulating’ means having transparency and heat-insulating property at the same time. Herein, for example, transparency is referred to as a light transmittance in the visible light spectrum region of at least 60% based on quartz, and heat-insulating property is referred to as a heat conductivity of 0.15 W/mk or less.
As used herein, ‘optical resin’ means a resin having light transmittability, particularly a resin having a light transmittance in the visible light spectrum region of at least 60%, at least 90%, at least 92%, or 92-98% based on quartz.
In example embodiments, there is provided a transparent heat-insulating material, such as a transparent heat-insulating film, including a transparent heat-insulating resin layer. The transparent heat-insulating resin layer includes an optical resin and polymer capsules.
According to an example embodiment, there is provided a transparent heat-insulating film (or sheet) including a substrate, and a transparent heat-insulating resin layer formed on the substrate.
As shown in
According to an example embodiment, the optical resin is a resin having light transmittability so that it is applicable to a transparent heat-insulating film. The optical resin may have a light transmittance in the visible light spectrum region of at least 60%, particularly at least 90%, more particularly at least 92% or 92-98% based on quartz
Various materials may be used as an optical resin as long as it has light transmittance within the above-defined range. For example, polyacrylic, polyolefin, polyurethane or polyepoxy resins, etc. may be used if the resin has the above-defined light transmittance. In addition, the optical resin may be a photocurable resin or thermosetting resin.
According to an example embodiment, it is required that the optical resin does not dissolve polymer capsules therein. Polymer capsules may be dispersed in the optical resin, preferably with no agglomeration, and more preferably with a random size distribution and no agglomeration, thereby forming a transparent heat-insulating resin layer.
According to an example embodiment, the polymer capsules are made of a polymer and may have a vacant space inside thereof. For example, at least a part of or the whole part of the polymer capsules may include a vacant space in the capsules, and a polymer film may surround the vacant space. Herein, the vacant space may be filled with gas.
As a non-limiting example, the polymer capsules may contain air (or an air layer) or contain an inert gas (or a gas layer), such as argon or krypton, etc. having a low heat conductivity.
When the transparent heat-insulating film includes such polymer capsules, its heat conductivity may be lowered as compared to the film without the polymer capsules, and transmission of radiative heat of solar radiation energy introduced from outside may be decreased and improve the shielding ratio of radiative heat rays. In addition, it is possible to reduce discharge or loss of heat occurring during the indoor heating.
Since the polymer capsules are made of a polymer, it is easy to carry out size control unlike inorganic capsules. The polymer capsules affect not only the heat-insulating property but also the transparency of a transparent heat-insulating film. According to example embodiments, since size of polymer capsules is controllable, it is easy to control the heat-insulating property and transparency of a transparent heat-insulating film.
The transparent heat-insulating film including the polymer capsules and the optical resin may show a light transmittance in the visible light spectrum region of at least 60%, particularly at least 63%, and more particularly at least 70% based on quartz.
In addition, while the transparent heat-insulating film including the polymer capsules and the optical resin has the above-defined light transmittance, at the same time it may show a high heat-insulating quality such as a heat conductivity of less than 0.2 W/mK, preferably 0.02-0.15 W/mK. Further, the transparent heat-insulating film may show substantially no optical distortion. Therefore, the transparent heat-insulating film may substitute for a glass window or may be attached to a glass window. The presence of optical distortion may be evaluated by measuring haze. For example, haze may be measured through a haze meter or spectrometer. According to an example embodiment, the transparent heat-insulating film may have a haze of 0.1% or less.
The polymer used for the polymer capsules is selected so that the above-defined light transmittance may be satisfied, considering the optical resin used together with the polymer capsules.
According to an example embodiment, the polymer capsules may have a difference in refractive index of 0-0.1 from that of the optical resin in view of light transmittance, haze. For example, the refractive index may be measured by using an Abbe refractometer. As such, it is possible to control the transparency of a transparent heat-insulating material by controlling a difference in refractive index between the polymer capsules and optical resin.
According to an example embodiment, the polymer of polymer capsules and the optical resin should be selected to satisfy the above-defined difference in refractive index. The polymer of polymer capsules may be selected from polyacrylic (e.g. poly(methylmethacrylate)), polystyrene, polyurethane, polycarbonate, polyolefin, and polyimide polymers etc.
According to an example embodiment, the content of polymer capsules in the optical resin layer may be more than 0 wt % and 90 wt % or less based on 100 wt % of the total weight of the polymer capsules and the optical resin. Although the content of polymer capsules may be increased in order to improve heat-insulating quality, transparency may be degraded in this case. On the other hand, when reducing the content of polymer capsules, transparency may increase but heat-insulating property may be degraded.
From the viewpoint of the heat-insulating property (e.g. a heat conductivity of 0.02-0.15 W/mK) and transparency (e.g. a light transmittance in the visible light spectrum region of at least 60% based on quartz), the content of polymer capsules may be 0.1 wt %-60 wt % based on 100 wt % of the total weight of the polymer capsules and the optical resin. More particularly, the content of polymer capsules may be 10 wt %-50 wt % based on 100 wt % of the total weight of the polymer capsules and the optical resin. This is because when the transparent heat-insulating film includes the polymer capsules within the above range, it may show substantially the same transparency (a difference in transparency within 1%) as the film without polymer capsules, while ensuring excellent heat-insulating property (e.g. a heat conductivity of 0.02-0.15 W/mK).
According to an example embodiment, the substrate is used as a support for forming the transparent heat-insulating resin layer.
According to an example embodiment, the transparent heat-insulating material may be a transparent heat-insulating film, and the transparent heat-insulating film may include a substrate and a transparent heat-insulating resin layer, and the transparent heat-insulating film may be used without substrate by removing the substrate after forming the transparent heat-insulating resin layer on the substrate.
According to an example embodiment, when the transparent heat-insulating film includes a substrate, the transparent heat-insulating resin layer may be formed on either side or both sides of the substrate. As well, the transparent heat-insulating resin layer may be interposed between two substrates.
According to an example embodiment, the substrate may have a light transmittance in the visible light spectrum region of at least 60% based on quartz. For example, a transparent substrate such as glass or polyethylene terephthalate may be used as a substrate.
In example embodiments, there is also provided a method for producing the above-described transparent heat-insulating material.
The method may include: preparing polymer capsules; and mixing the polymer capsules with an optical resin.
According to an example embodiment, provided is a method for producing a transparent heat-insulating film that may include: preparing polymer capsules; and mixing the polymer capsules with an optical resin, and coating the substrate with a resultant mixture to form a transparent heat-insulating resin layer provided on the substrate.
According to an example embodiment, the method may further include removing the substrate after the coating.
According to an example embodiment, the polymer capsules may be prepared in various ways.
As a non-limiting example, the method may include: mixing and heating a surfactant, dispersant, organic solvent, radical polymerizable monomers and a radical polymerization initiator to provide polymer capsules; and mixing the polymer capsules with an optical resin, and coating a substrate with a resultant mixture.
Hereinafter, each of the above-mentioned ingredients will be explained in detail.
The surfactant may form spherical reverse micelles when it is dissolved in an organic solvent. It is possible to control size of reverse micelles formed in the solution depending on a ratio of surfactant. In light of this, the surfactant has to be used in such an amount that allows formation of reverse micelles. Further, since formation of reverse micelles affects formation of polymer capsules, it is possible to control a size of polymer capsules by adjusting the size of reverse micelles as mentioned above.
The organic solvent may serve as a solvent for forming reverse micelles. For example, a polar organic solvent, such as methanol etc., may be used.
Particular non-limiting examples of the surfactant that may be used include dioctyl sulfosuccinate sodium salt (AOT), or the like.
The initiator may be used for a radical polymerization. When radicals and a small amount of monomers dissolved in solution join with each other, initiation occurs. The initiated radicals may grow in solution, and have surface activity from the time point where the balance between the hydrophilic moiety of initiator and the hydrophobic moiety of monomers is maintained adequately.
Particular non-limiting examples of the initiator that may be used include 2,2′-azobisisobutyronitrile (AIBN), or the like.
Explaining the dispersant, oligoradicals grown from the radicals of initiator after the initiation of polymerization may be separated and precipitated from the continuous phase as their sizes increase. The preliminary particles thus precipitated may be stabilized by the dispersant and absorb a larger amount of monomers as the particle size increases, and thus they may be grown as particles. Particular non-limiting examples of the dispersant that may be used include poly(vinylpyrrolidone) (PVP), or the like.
Meanwhile, radical polymerizable monomers may react continuously with the radicals generated by the initiator during the polymerization, and grow to be polymer capsules. Particular non-limiting examples of the monomers that may be used include methyl methacrylate (MMA), or the like.
According to an example embodiment, the method may include carrying out freeze-drying after the polymerization of polymer capsules. Freeze-drying may prevent agglomeration of capsules during washing and drying of the capsules. Thus, freeze-drying may facilitate homogeneous dispersion of capsules in the optical resin without agglomeration (aggregates).
More particularly, according to an example embodiment, the method may include: mixing a surfactant, dispersant and an organic solvent; adding radical polymerizable monomers and a radical polymerization initiator to a resultant mixture and then heating the mixture to polymerize polymer capsules; freeze-drying the polymer capsules; and mixing freeze-dried polymer capsules with an optical resin and coating a substrate with a resultant mixture.
According to an example embodiment, when the optical resin is a photocurable or thermosetting resin, curing may be carried out by light irradiation (e.g. using a UV lamp) or by heating after the coating operation.
According to an example embodiment, the method may allow easy control of the size (average size) of the polymer capsules.
For example, in case of radical polymerization, it is possible to obtain capsules having a uniform size as well as random sizes by adjusting the homogeneity of capsules depending on time. That is, according to an example embodiment, when carrying out polymerization of polymer capsules, capsule formation may begin 2 hours after the reaction starts and capsules with a uniform size may be formed during this time. After the lapse of 7 hours from the start of reaction, capsules with random sizes may be formed. In addition, when the reaction is carried out for 10 hours or more, capsules with random sizes may be converted into capsules with a uniform size so as to reach equilibrium. Thus, it is possible to polymerize capsules with a uniform size as well as capsules with random sizes by adjusting the time required for polymerizing polymer capsules.
Accordingly, it is possible to obtain polymer capsules having an average particle size of 0.1-150 μm, for example.
According to an example embodiment, the polymer capsules may have random particle sizes. As compared to polymer capsules with a uniform size (i.e., the case where the capsules having one average particle size are present), polymer capsules with random sizes (i.e., the case where capsules having at least two different average particle sizes are mixed) may have lower heat conductivity, and thus are better in terms of heat insulation. When polymer capsules having different sizes (different average sizes) are mixed, a larger amount of polymer capsules may be present in the same volume than polymer capsules with a uniform size. This results in lower heat conductivity. From the viewpoint of heat insulation, lower heat conductivity means better heat insulation. Therefore, if polymer capsule is contained in the same content, capsules with random sizes (the case where polymer capsules having at least two different average particle sizes are mixed) may show similar transparency but better heat-insulating property as compared to capsules with a uniform size.
According to an example embodiment, additives may be further introduced when preparing the transparent heat-insulating film.
For example, metallic materials or ceramic materials may be used as additives to provide a heat-shielding function through light reflection or light absorption. When using such light reflective or light absorptive additives, it is possible to maximize heat shielding through light reflection or absorption in addition to said heat-insulating property of the transparent heat-insulating film. Such light reflective or light absorptive additives may be incorporated together with the polymer capsules to the transparent heat-insulating resin layer or may be formed as a separate layer.
That is, according to an example embodiment, the transparent heat-insulating film may include: a substrate; a transparent heat-insulating resin layer formed on either side or both sides of the substrate; and a layer including a light reflective or light absorptive additive and formed on the transparent heat-insulating resin layer or on the substrate where transparent heat-insulating resin layer is not formed thereon.
The additive or additive layer is added or formed in such a manner that the transparency of the whole transparent heat-insulating film is not degraded. Particular non-limiting examples of the additives that may be used include nanoparticles such as ceramic nanoparticles or metal nanoparticles.
The transparent heat-insulating film obtained as disclosed herein may include polymer capsules therein and have high heat-insulating property, and thus it may reduce transmission of radiative heat of solar radiation energy entering from the exterior and prevent discharge or loss of heat when indoor heating, while showing high transparency as well. Therefore, the transparent heat-insulating film disclosed herein may be very useful as a heat-shielding or heat-insulating film for windows of buildings (particularly, glass-walled buildings), houses, cars, or the like.
The examples and experiments will now be described. The following examples and experiments are for illustrative purposes only and not intended to limit the scope of the present disclosure.
Preparation of Polymer Capsules
Methyl methacrylate (MMA) (10 wt %), dioctyl sulfosuccinate sodium salt (AOT) (0.45 wt %), poly(vinylpyrrolidone) (PVP) (4 wt %), 2,2′-azobisisobutyronitrile (AIBN) (0.1 wt %) and methanol (85.45 wt %) are mixed in a weight ratio of 10:0.45:4:0.1:85.45.
Particularly, to carry out polymerization of polymer capsules, a three-necked flask is purged with argon, AOT (0.45 wt %, 0.9 g), PVP (4 wt %, 4 g) and MeOH (85.45 wt %, 108 mL) are introduced thereto, and the reaction mixture is agitated under 1000 rpm for about 10 minutes until the materials are dissolved completely. To the resultant mixed solution, MMA monomer (10 wt %, 10 g) and AIBN (0.1 wt %, 0.1 g) are added, and the mixture is agitated under 400 rpm at 58° C. The solution, which originally is transparent, becomes turbid when the reaction starts. After the lapse of 2 hours from the start of reaction, formation of MMA capsules begins, wherein dented capsules with a uniform size are formed. After the lapse of 7 hours from the start of reaction, capsules with random sizes are formed. In addition, after the lapse of 10 hours or more from the start of reaction, the capsules with random sizes are converted into capsules with a uniform size in order to maintain a stable state. The PMMA capsules thus obtained are washed with deionized water three times, and subjected to centrifugal separation. This allows removal of unreacted monomers and solvent. The resultant PMMA capsules may be subjected to freeze-drying to obtain capsules in the form of fine powder.
As can be seen from
Production of Transparent Heat-Insulating Film
An optical resin (acrylic resin) is mixed with the spherical polymer capsules obtained as described above in an amount of 0 wt % (Comparative Example), 10 wt % (Example 1), 20 wt % (Example 2) and 30 wt % (Example 3).
The polymer capsules and the optical resin have a refractive index of 1.49361 and 1.5, respectively, as measured by using an Abbe refractometer.
Meanwhile, a sheet of PET film is prepared and the mixture of optical resin with polymer capsules is dropped onto the PET film and coated by using a bar coater. The coating is carried out by setting the bar coater to the conditions of a coating thickness of 80 μm and a coating speed of 4 mm/s.
The film thus obtained is subjected to photocuring by light irradiation using a UV lamp for 2 minutes.
As shown in
Meanwhile,
Heat conductivities of each transparent heat-insulating films according to Comparative Example and Examples 1-3 are measured by using a heat conductivity tester three times, and the average value is calculated.
As can be seen from
As described above, according to example embodiments, it is possible to provide a transparent heat-insulating film having excellent heat-insulating property while showing high transparency as well. In addition, it is possible to control the size of capsules contained in a transparent heat-insulating film with ease, and the transparent heat-insulating film may be obtained through a simple and easy process, which is cost-efficient and suitable for mass production. Further, it is possible to control the light transmittability and heat-insulating property of a transparent heat-insulating film with ease.
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| Number | Date | Country | |
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| 20160069069 A1 | Mar 2016 | US |
