JPS6319212B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an adsorbent for double-glazed glass, and more particularly, the present invention relates to an adsorbent for double-glazed glass, and more particularly, an adsorbent that can effectively prevent condensation of water vapor and organic solvent vapor within the double-glazed glass space, and also effectively prevent dust generation from the adsorbent. This invention relates to an adsorbent for double glazing. Conventionally, double-glazed glass assemblies, which are made by bonding the periphery of multiple glass plates with adhesive through a spacer member containing a desiccant, have been used in various buildings as window glass with excellent heat insulation and soundproofing effects. It is used. A problem with this double-glazed glass is that when the air temperature in the space between the glass panes drops below the dew point, steam condenses, thereby impairing visibility through the window glass. This kind of vapor condensation is not only the water vapor in the air that originally exists between the glasses or the water vapor contained in the air leaking from between the spacer member and the glass, but also the water vapor contained in the adhesive and evaporates over time. It is known to be generated by organic solvent vapor. Synthetic zeolite, activated alumina, silica gel, etc. are known to be used as desiccants or adsorbents to adsorb these vapors, but these adsorbents do not work well in systems where water vapor and organic solvent vapor coexist. Despite wide variations in temperature,
It is still not sufficient for the purpose of adsorption and removal to prevent so-called tracking. For example, among the adsorbents mentioned above, silica gel is said to be suitable for adsorbing organic solvent vapor, but silica gel preferentially adsorbs water selectively in systems where water coexists with organic solvents. There is a tendency, and its effectiveness is questionable. From this point of view, it has already been proposed to use a combination of multiple types of adsorbents as adsorbents for double glazing. , the use of a combination of silica gel, activated alumina, activated carbon, or a mixture thereof, which are adsorbent to hydrocarbons, is disclosed. Furthermore, in the case of activated carbon, since its color is unusual, it is difficult to remove the activated carbon from the spacer. It is suggested that care must be taken to avoid the occurrence of In addition to the above-mentioned adsorption performance in a system where water vapor and organic solvent vapor coexist, adsorbents for double-glazing glass have the problem of dust generation from the adsorbent. In other words, zeolite, activated carbon, etc., are likely to generate dust, even if the strength varies, due to vibrations applied during transportation of double-glazed glass, during construction, or when used as window glass, and these dusts are likely to generate dust on the spacer member. There are disadvantages such as entering the space between the glasses through the suction opening and adhering to the glass surface, impairing visibility or becoming a core that promotes fogging. Conventionally, there have been several proposals regarding adsorbents for double-glazing glass, but as far as the present inventors are aware, there have been almost no proposals regarding prevention of such dust generation. Therefore, an object of the present invention is to provide a double-glazed glass that exhibits excellent adsorption performance for water vapor and organic solvent vapor within a double-glazed glass space, and that effectively prevents the generation of dust even when subjected to harsh handling. To provide adsorbents for Another object of the present invention is to provide an adsorbent for coated glass which is composed of a combination of granular zeolite and granular activated carbon and in which these granules have a coating structure. According to the invention, a core consisting of a synthetic zeolite-clay binder mixture containing a synthetic zeolite in a higher than average content and a synthetic zeolite-clay binder containing a clay binder in a higher than average content is provided. A mixture containing granular zeolite with a shell consisting of a mixture of quality binders and granular activated carbon having a synthetic resin latex coating agent on the surface of 1 to 20% by weight per activated carbon in a weight ratio of 80:20 to 50:50. An adsorbent for double glazing is provided, characterized in that it consists of: Granular Zeolite In FIG. 1 showing the cross-sectional structure of the granular zeolite used in the present invention, the granular zeolite 1 has a cross-sectional structure consisting of a core 2 and a shell 3.
The remarkable feature of this granular zeolite is that the core 2 contains synthetic zeolite in a larger proportion than the average content, and the shell 3 contains a clay binder in a larger proportion than the average content. . That is, compared to conventional granular zeolite in which synthetic zeolite and clay binder are present in a uniform and uniform composition ratio over the entire cross section, the content ratio of clay binder in the shell is higher than the average content. As a result, this granular zeolite exhibits significantly improved powder resistance (wear resistance) and compressive strength.Furthermore, by increasing the amount of synthetic zeolite in the core compared to the average content, this granular zeolite Zeolites exhibit zeolitic properties such as a combination of superior adsorption rate and adsorption capacity. Thus, an improvement in the combined mechanical and zeolitic properties of the granular zeolite is achieved even when the shell thickness is extremely small. In this granular zeolite, the fact that the shell is formed from a mixture of a clay binder and a synthetic zeolite is also important from the viewpoint of adsorption speed, and in fact, compared to a granular zeolite in which the shell is composed only of a clay binder, It is observed that the granular zeolites used in the present invention exhibit significantly improved adsorption rates. This seems to be because the synthetic zeolite present in the shell acts as a passage for the substance to be adsorbed. It is also important that the core is made of a mixture of synthetic zeolite and clay binder in order to increase the strength of the granular zeolite as a whole. However, in the granular zeolite used in the present invention, compared to conventional granular zeolite with the same level of powder resistance (wear resistance) and compressive strength, the overall clayey binder content is significantly reduced, Furthermore, adsorption speed and adsorption capacity can be significantly improved, and conversely, dusting resistance (wear resistance) and compressive strength can be significantly improved compared to conventional granular zeolite with the same level of adsorption capacity. It should be understood that In the granular zeolite used in the present invention, the ratio of core to shell varies slightly depending on the particle size and grain size of the granular zeolite, but generally speaking, it is 99:1 to 80:20, particularly 98: 2 to 85:15
The weight ratio should be within the range of . That is, when the ratio of shells is less than the above range, mechanical properties such as powder resistance tend to deteriorate, and when it exceeds the above range, zeolite properties such as adsorption properties tend to deteriorate. When the overall particle size of the granular zeolite is large, the shell content ratio can be set in a relatively small range within the above range, and when the particle size is small, it can be set in a larger range. In the present invention, the mixture constituting the core 2 is
It contains synthetic zeolite and clayey binder in a weight ratio of 90:10 to 60:40, especially 88:12 to 70:30, while the mixture constituting Shell 3 contains clayey binder and synthetic zeolite in a weight ratio of 95:10 to 60:40. 5 to 30:
70, in particular in a weight ratio of 70:30 to 50:50, and said shell contains at least 10% more clay binder than said core composition, in particular at least 15% more by weight, Desirable for its combination of mechanical strength and zeolitic properties. In the present invention, as the synthetic zeolite, zeolite A, zeolite It can exist in any form. The particle size of the synthetic zeolite powder can generally range from 0.01 to 100 microns, particularly from 0.1 to 50 microns. As the clay binder, kaolin group clay minerals such as kaolin; palygorskite group clay minerals such as attapulgite; smectite type clay minerals such as acid clay, montmorillonite, bentonite, or allofene may be used alone or in combination of two or more types. It can be used. The particle size of the clayey binder can range from 0.1 to 10 microns, especially from 0.5 to 5 microns. In producing the granular zeolite of the present invention, a synthetic zeolite-clay binder mixture having the above-described core-forming composition is granulated into cores using an aqueous solution of a water-soluble polymer binder as a granulation medium. The mixture of the synthetic zeolite and the clay binder can be produced by dry blending using a known mixer such as a ribbon blender, unical blender, Henschel mixer, or the like. The mixture may be granulated using any known granulation method using the aqueous solution as a granulation medium, such as rolling granulation, extrusion granulation, spray granulation, tablet granulation, fluidization granulation, etc. It can be done with In terms of mechanical strength of the granular zeolite, the rolling granulation method is particularly preferable, and the above-mentioned synthetic zeolite
Granulation is carried out by preparing seed particles of a clayey binder mixture and depositing powder of the mixture thereon while moistening the seed particles with a granulation medium to cause grain growth. The water-soluble polymer binder has a solid content of 0.01% per total amount of synthetic zeolite-clay binder.
It can be used in amounts of from 5% to 5% by weight, in particular from 0.05 to 2% by weight, while aqueous solutions as granulation medium may contain from 20 to 70% by weight, depending on the granulation means.
It is preferred to use amounts of 30 to 60% by weight. Examples of water-soluble polymer binders include starch, cyanoethylated starch, carboxymethyl starch, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, vinyl ether maleic acid copolymer, sodium alginate, sodium lignin sulfonate, gum arabic, gum tragacanth, etc. Can be used. The core particles obtained in the above-described process are dry blended with a powder mixture of synthetic zeolite and clay binder whose composition falls within the shea-forming range to form a coating of the powder mixture on the particle surface. The amount of the powder mixture blended into the core particles is already in the range mentioned above, and the core particles formed by the above-mentioned method still contain a solution as a granulation medium inside, and this solution makes the powder The particles adhere firmly to the surface of the core particles to form a coating.
The dry blending of the core particles and powder mixture is preferably carried out in a tumble granulator containing the produced core particles.
This can be easily carried out by charging the powder mixture once or in portions and operating the apparatus. In the present invention, the synthetic zeolite and clay binder forming the shell may be the same or different from the synthetic zeolite and clay binder forming the core. In this way, core-shell structured granules are prepared, which are air-dried and then calcined at temperatures of 300-650°C for 10-300 minutes to sinter the granules into the final granular zeolite. It is generally desirable that the granular zeolite have a particle size of 5 to 32 meshes (Tyler standard). Granular Activated Carbon In FIG. 2 showing the cross-sectional structure of the granular activated carbon used in the present invention, the granular activated carbon 4 consists of a granular activated carbon body 5 and a synthetic resin latex coating 6 formed on its surface. Since this coating 6 is formed from synthetic resin latex, it has the remarkable feature that it does not substantially reduce its adsorption to organic solvents, and furthermore, it significantly suppresses the generation of dust. will become immediately clear from the results of the examples below. The reason why the powder resistance of the granular activated carbon used in the present invention can be improved without a significant decrease in adsorption to organic solvents is not fully clear, but since the coating 6 is derived from synthetic resin latex, It is a film or netting with countless pores that allows the vapor of the organic solvent to pass through, but it acts as a sufficient film to prevent the activated carbon from being worn out, and this film also acts as a cushioning material that absorbs shock, etc. It is presumed that there is a cause for this effect. The granular activated carbon body used in the present invention may be obtained from coal, petroleum residue, charcoal, fruit shells, etc., by either a gas activation method such as steam or carbon dioxide, or a chemical activation method such as zinc chloride or phosphoric acid. ,
Spherical, cylindrical, or irregularly shaped granular activated carbon with a BET specific surface area of 500 to 2000 m ² /g and a particle size of 4 to 30 mesh can be used, but spherical activated carbon are particularly preferably used. The coating agent for synthetic resin latex is an aqueous emulsion of synthetic resin, and for example, the following can be used alone or in combination of two or more. (1) Butadiene polymers or copolymers of butadiene and styrene, styrene derivatives, acrylonitrile, methacrylonitrile, isoprene, isobutylene, etc. (2) Copolymers of isoprene, styrene, and styrene derivatives. (3) Chloroprene polymers or copolymers of chloroprene and styrene, styrene derivatives, acrylonitrile, and isoprene. (4) Copolymers of acrylic esters and styrene, styrene derivatives, vinyl chloride, vinyl acetate, acrylonitrile, and ethyl methacrylate. (5) Methacrylnitrile polymers and copolymers of methacrylnitrile and styrene, etc. (6) Vinyl acetate polymer, vinyl chloride polymer. These may be subjected to appropriate modification treatment such as carboxy modification. The amount of latex used is 1 to 20% by weight, preferably 2 to 5% by weight as a latex solid content based on the weight of the activated carbon body. When the amount of latex used is less than 1% by weight, there is no effect of reducing the fineness, and when it is more than 20% by weight, the effect of reducing the fineness is great, but the gas adsorption performance is greatly reduced, which is not preferable. The solid content concentration of the latex water emulsion used is suitably 10 to 50% by weight, and the amount of liquid used is preferably 0.2 to 1.0% based on the weight of activated carbon. The coating on the activated carbon surface can be applied by spraying a latex emulsion liquid in an appropriate manner or by impregnating it with activated carbon, and then,
Dry at 100-150°C to obtain low-pulverization granular activated carbon. Combination adsorbent According to the present invention, the granular zeolite treated to be powder-resistant as described above and the granular activated carbon are mixed in a weight ratio of 80:20 to 50:50, particularly in a weight ratio of 70:30 to 50:50. Mix and use as adsorbent for double glazing. In other words, the granular zeolite of the present invention has the characteristic that it has an extremely large amount of water adsorption even when the humidity is extremely low, and furthermore, it has a property that it has a very large amount of water adsorption even when the humidity is extremely low, and furthermore, it has almost no H ₂ O specific pressure (water vapor pressure per saturated water vapor at 20°C). It has the characteristic that the amount of moisture adsorbed is constant regardless of the amount of moisture. On the other hand, granular activated carbon has a significantly larger adsorption amount for organic solvents such as xylene and methyl ethyl ketone than other adsorbents, and similarly, the adsorption amount of organic solvents is almost constant regardless of the organic solvent vapor specific pressure. It has the characteristic that Furthermore, granular activated carbon has the property of selectively adsorbing organic solvents regardless of the presence of water vapor. Thus, according to the present invention, by using granular zeolite and granular activated carbon in the above-mentioned ratio, vapor components within the double-glazed glass can be adsorbed most effectively.
Despite significant changes in temperature, condensation and fogging on the glass can be stably prevented over a long period of time. In addition, the granular zeolite and granular activated carbon used in the present invention not only have excellent powder resistance even when subjected to harsh handling, but also have excellent powder resistance when these different materials are mixed together. It has excellent properties, and hardly any dust is generated even during harsh handling. In addition to the above-mentioned essential components, the adsorbent for double-glazed glass of the present invention can contain other adsorbents as desired. In one embodiment of the present invention, when granular alumina-silica gel is blended in an amount of 10 to 70% by weight, particularly 20 to 60% by weight, based on the total amount of granular zeolite and granular activated carbon, water adsorption properties under high humidity conditions are further improved. Therefore, an adsorbent for double-glazing glass having even better adsorption properties can be obtained. Such granular alumina-silica gels are known per se, and those described in, for example, Japanese Patent Publication Nos. 38-17002, 40-16347, and 47-8446 are preferably used. The invention is illustrated by the following example. Reference Example 1 As the core part of spherical zeolite, mix 20 parts by weight of kaolin 150°C dry powder with 80 parts by weight of 4A type synthetic zeolite 150°C dry powder, mix thoroughly in a V-shaped mixer, A mixed powder of synthetic zeolite and kaolin was produced. Approximately 25 kg of the obtained mixed powder was placed in a rolling granulator, and rolled and molded while spraying water with a spray nozzle, and then sieved to remove the powder and form a spherical molded product with a size of 0.25 to 0.5 mm. I made this the core. These cores were rolled in a rolling granulator, and while gradually adding the mixed powder prepared earlier and a 0.5% aqueous solution of sodium ligninsulfonate, a zeolite layer was grown on the surface of the cores over a period of 2 hours, resulting in a wet spherical shape. A zeolite core was produced. Next, 60 kg of the spherical zeolite core obtained by the above method was placed in a rolling granulator, and 3 kg of a powder made by thoroughly mixing 50 parts by weight of 4A type synthetic zeolite powder and 50 parts by weight of kaolin powder for the shell part was added. After that, rolling was continued for another 5 to 10 minutes to coat the surface and obtain a granulated product with a spherical diameter of 0.5 to 3.0 mm. The wet spherical zeolite thus obtained was air-dried (naturally dried), dried in an atmosphere of 100 to 150°C for 3 hours, sieved, sized to 10 to 20 mesh (0.50 to 0.83 mm), and then sized to 550 A product was obtained by baking at ±30°C for 3 hours. Performance tests were conducted on the wear-resistant zeolite thus obtained by the following method, and the following results were obtained. 1. Powderization rate measurement method: Samples left at room temperature for 48 hours to fully absorb moisture.
50 g was placed in a standard sieve (JIS Z-8801), which was attached to a shaker, and subjected to rotational motion of the shaker and impact force of a hammer for 30 minutes, and the weight loss of the sample was measured to determine the pulverization rate. Powdering rate (%) = Sample collection amount - Post-test test weight / Sample collection amount Sample container: Standard sieve (JIS Z-8801) (diameter
15cm) Layer the 28 mesh, 60 mesh, and 4 mesh sieves in order and place the sample into the 28 mesh sieve. Amount of sample collected: 50g of sample after absorbing moisture Shaker: According to JIS6002 (1978) Number of revolutions: 290 times/min Number of impacts: 156 times/min2 Measurement results

[Table] Reference Example 2 This reference example explains the method for producing viscous activated carbon and its characteristics. Coal-based spherical activated carbon with a particle size of 10 to 32 mesh and a BET specific surface area of 1080 m ² /g was prepared by diluting 100 g of synthetic rubber latex (SBR - carboxyl group modification, solid content concentration 47% by weight) with water. 25 ml of the liquid adjusted to a type concentration of 20% by weight was sprayed with a hand sprayer while stirring the activated carbon, and then dried in a dryer (air open) at 100°C to obtain low-pulverized carbon. A performance test was conducted on the thus obtained low pulverized coal by the following method, and the following results were obtained. 1. Abrasion resistance strength The abrasion resistance was measured by the microstrength method, the powdering rate of activated carbon particles was determined, and the results were compared with an untreated product (control product). Microstrength measurement conditions Sample container φ25mm x 30mmH (stainless steel cylinder with internal volume of 150ml) Sample filling amount 50ml Rotation speed 20RPM Rotation time 30min Total rotation speed 600Round Calculation method of powdering rate Powdering rate = sample weighed amount - measurement Weight of sample after measurement/amount of sample weighed Both the samples before and after measurement are samples that were sieved for 5 minutes using a rotary tap machine using a 32-mesh sieve and remained on the sieve. 2 Measurement results

[Table] Example 1 Type 4A spherical zeolite produced in Reference Example 1 ( Particle size 10-20 mesh) 50% by weight
Low powder spherical activated carbon (particle size
20 g of a 50% by weight mixture (10-20 mesh) was filled. Next, a spacer filled with desiccant was made in the same way, and the corners were connected with corner keys to create a 1 meter x 1 meter double-glazed window frame (80 g of desiccant was filled on each side). Next, thoroughly clean the glass connection part of the spacer with a piece of cloth soaked in toluene, and after drying, adhere one side of the double-sided adhesive tape and apply a
Glass measuring 1 meter x 1 meter in millimeters was glued together. A similar operation was performed on the other side of the spacer to adhere the glass. Next, in order to bond and seal the glass plates, polysulfide-based (thiokol) liquid polymer and vulcanizing agent (lead peroxide) are thoroughly kneaded in a ratio of 100:10 as a sealant, and the spacer and glass are bonded together using a sealing gun. The sealant was filled into the space and left indoors for 24 hours to harden the sealant and create double-glazed glass. Next, the double glazing glass produced by the above method is JISR
The dew point was tested using the dew point test method described in 8.4 of 3209 (1979). In addition, in order to observe the phosphing phenomenon caused by organic solvents and sealant decomposition products, a separate 30 cm x 30 cm double glazing glass was used (1/3 amount of desiccant was used for a 1 meter x 1 meter double glazing glass). (27 g packed on each side) was prepared, placed in an air oven, heated and cooled repeatedly between 80°C and room temperature for 10 days, and visually observed for the presence or absence of fogging. The results are shown in Table-1. Next, as a comparative example, type 4A spherical zeolite (particle size 10 to 20
mesh) 50% by weight and spherical silica gel (particle size 10~
A spacer was filled with 20 g of a 50% by weight mixture (80 g on four sides), and the same operation was performed to produce double-glazed glass and a dew point test was conducted. In addition, in order to observe the phogging phenomenon caused by organic solvents and sealant decomposition products, 30
A similar operation was performed using double-glazed glass measuring 30 cm x 30 cm, and the presence or absence of fogging was observed with the naked eye. The results are shown in Table-1.

[Table] Next, the pulverization rate of the mixture of type 4A spherical zeolite and spherical activated carbon used as a desiccant was measured by the method of Reference Example 1 and Reference Example 2. As a result, the powderization rate was 0 (%) in either method. Example 2 In a room at a temperature of 25°C and relative humidity of 50%, 4A type spherical zeolite (particle size 10 ~20 mesh) 50% by weight
Silica/alumina gel manufactured by Mizusawa Chemical Industry Co., Ltd. (particle size 10
20 g of a mixture of 30 wt.
filling). Thereafter, the same operations as in Example 1 were performed to produce double-glazed glass. Next, a dew point test was conducted using the dew point test method described in JIS R-3209 (1979) 8.4. In addition, in order to observe the fogging phenomenon caused by organic solvents and sealant decomposition products, we separately prepared a 30 cm x 30 cm double-glazed glass (27 g of desiccant on each side) and placed it in an air oven at 80°C. Heating and cooling were repeated at room temperature for 10 days, and the presence or absence of fogging was visually observed. The results are shown in Table-2. Next, as a comparative example, type 4A spherical zeolite (particle size 10 to 20
mesh) 80% by weight and spherical silica gel (particle size 10~
Fill a spacer with 20g of the 20wt% mixture (filling 80g on 4 sides) and perform the same operation to produce double-glazed glass, JISR-3209 (1979)
The dew point test was conducted according to 8.4. In addition, in order to observe the phogging phenomenon caused by organic solvents and sealant decomposition products, 30
A similar operation was performed using double-glazed glass measuring 30 cm x 30 cm, and the presence or absence of fogging was observed with the naked eye. The results are shown in Table-2.

[Table] Next, the pulverization rate of the mixture of 4A type spherical zeolite, spherical silica/alumina gel, and low-pulverization activated carbon used as a desiccant was measured by the method of Reference Example 1 and Reference Example 2. As a result, the powderization rate was 0 (%) in either method.

[Brief explanation of the drawing]

Fig. 1 is a diagram showing the cross-sectional structure of the granular zeolite used in the present invention, Fig. 2 is a diagram showing the cross-sectional structure of the granular activated carbon used in the present invention, and Fig. 3 is a cross-sectional diagram of the double-glazed glass used in Example 1. The numbers in the drawings indicate dimensions (unit: mm). Reference code 1 is granular zeolite, 2 is core, 3 is shell, 4 is granular activated carbon, 5 is activated carbon body, 6 is synthetic resin latex coating, A is desiccant, B is spacer, C is double-sided adhesive tape, D is sealing Agent and E indicate glass, respectively.

Claims (1)

[Scope of Claims] 1 Synthetic zeolite containing synthetic zeolite in an amount greater than the average content - a core consisting of a mixture of clay binders, and a synthetic zeolite containing clay binder in an amount greater than the average content - granular zeolite with a shell consisting of a mixture of clayey binders, and granular activated carbon having a synthetic resin latex coating agent on its surface of 1 to 20% by weight per activated carbon in a weight ratio of 80:20 to 50:50. An adsorbent for double glazing, characterized in that it consists of a mixture. 2 The mixture contains 10 to 70% by weight of granular alumina based on the total amount of granular zeolite and granular activated carbon.
The adsorbent according to claim 1, characterized in that it contains silica gel. 3. The adsorbent according to claim 1, wherein the core and the shell in the granular zeolite are present in a weight ratio of 99:1 to 80:20. 4. The core of the granular zeolite contains synthetic zeolite and clay binder in a ratio of 90:10 to 60:40.
wherein the shell contains a clay binder and a synthetic zeolite in a weight ratio of 95:5 to 30:70, and the shell contains a clay binder in an amount of at least 10% by weight greater than the core composition. The adsorbent according to claim 1, characterized in that it contains: 5 Synthetic zeolite in granular zeolite is A
The adsorbent according to claim 1, which is a type zeolite, an X type zeolite, a Y type zeolite, or a synthetic mordenite. 6. The adsorbent according to claim 1, wherein the clayey binder in the granular zeolite is a kaolin type clay mineral, a palygorskite clay mineral, a smectite clay mineral, or allofene. 7 The active body in granular activated carbon is 500 to 500
The adsorbent according to claim 1, which has a BET specific surface area of 2000 m ² /g. 8. The adsorbent according to claim 1, wherein the coating agent of granular activated carbon is applied in the form of an aqueous emulsion.