JPH0345019B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a double-glazed glass assembly, and more particularly, it can effectively prevent condensation of water vapor and organic solvent vapor within the double-glazed glass space, and can also effectively prevent dust generation from adsorbents. The present invention relates to a double glazing assembly. Traditionally, double-glazed glass assemblies, which are made by joining multiple glass plates together with a sealant through a spacer member containing a desiccant inside, have been used in various types of construction as window glass with excellent heat and sound insulation effects. has been done. 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 type of vapor condensation is caused by not only water vapor in the air that originally exists between the glass or water vapor contained in the air leaking from between the spacer member and the glass, but also organic water vapor contained in the sealant that evaporates over time. It is known to be caused by 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 in systems where water and organic solvent coexist, silica gel selectively adsorbs water with priority. 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-glazed glass. , 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., can generate dust even if the strength differs due to vibrations applied during transportation of double-glazed glass, during construction, or when used as window glass, and these dusts can be used for spacer members. 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. The assembly is provided. Another object of the present invention is to provide a double glazing assembly containing a combination of coated granular zeolite and coated granular activated carbon as adsorbents in a spacer member having vapor adsorption openings. According to the present invention, in a double-glazed glass assembly in which a spacer member containing an adsorbent is positioned inside at least one side of the periphery of a plurality of glass plates, and the periphery is sealed with a sealant, the adsorbent is , a core consisting of a synthetic zeolite-clay binder mixture containing a greater than average content of synthetic zeolite, and a synthetic zeolite-clay binder mixture containing a greater than average content of clay binder. and granular activated carbon having a synthetic resin latex coating agent of 1 to 20% by weight per activated carbon on the surface, and the granular zeolite and the granular activated carbon are separated from each other in the spacer member A double glazing assembly is provided that is characterized in that it resides within a receiving space. The invention will be explained in detail below. In FIGS. 1 and 2 showing the structure of the double-glazed glass assembly of the present invention, a pair of glass plates 1a and 1b are
They are overlapped with spacer members 2 disposed on the four sides of the periphery. A double-sided adhesive tape 3 is placed between the side surface of the spacer member 2 and the inner surface of the glass.
are arranged, the spacer 2 and the inner surface of the glass are adhered, and a space 4 of a constant width defined by the spacer 2 is formed between the two glass plates 1a and 1b.
will be formed. A sealant 5 is applied to the periphery of this glass-spacer assembly, that is, to the outer periphery of the spacer 2.
A space 4 between a and 1b is sealed with a sealant 5. The spacer 2 has a hollow or cylindrical shape, and is arranged around the glass plates 1a and 1b.
At least one side of the side spacers 2 has an adsorbent 6 accommodated in its hollow interior. The spacer 2 containing the adsorbent 6 is provided with a small opening 7 for vapor adsorption that communicates with the space 4 . According to the present invention, by using a combination of coated granular zeolite and coated granular activated carbon, which will be described in detail below, as the adsorbent 6, the double-glazed space 4
By completely adsorbing internal water vapor and organic solvent vapor derived from sealants, it prevents clouding due to condensation of internal vapor at low temperatures, and even when subjected to harsh handling, it prevents dust generation and its accompanying effects. Various problems can be effectively solved. The coated granular zeolite and the coated granular activated carbon can be present in the double glazing assembly in any ratio, but preferably from 95:5 to 30:70, especially from 90:10 to 30:70.
Good results in terms of preventing condensation are obtained when present in a weight ratio of 40:60. Granular Zeolite In FIG. 3 showing the cross-sectional structure of the granular zeolite used in the present invention, the granular zeolite 11 has a cross-sectional structure consisting of a core 12 and a shell 13. A notable feature of this granular zeolite is that the core 12 contains synthetic zeolite in a larger proportion than the average content, and the shell 13 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 exhibited significantly improved powder resistance (wear resistance) and compressive strength, and by increasing the amount of synthetic zeolite in the core compared to the average content,
This granular zeolite exhibits 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 diameter of the granular zeolite, but generally speaking, it is in the range of 99:1 to 80:20. It is better to
Particularly preferred is a weight ratio of 90:2 to 85:15. When the amount ratio of shell is small, mechanical properties such as powder resistance tend to decrease, and when it is large, zeolite properties such as adsorption properties tend to decrease. When the overall particle size of the granular zeolite is large, the shell ratio can be in a relatively small range, and when the particle size is small, it can be in a larger range. In the present invention, the mixture constituting the core 12 is composed of synthetic zeolite and clay binder in a ratio of 90% to 90%.
10 to 60:40, in particular 88:12 to 70:30, while the mixture constituting Shell 3 contains clay binder and synthetic zeolite in a weight ratio of 95:5 to 70:30.
30:70, in particular from 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. is more desirable due to 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, alone or in combination of two or more. 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 synthetic zeolite and the clay binder may be mixed by dry blending using a known mixer such as a ribbon blender, conical blender, or Henschel mixer. This mixture is granulated using a known granulation method using the aqueous solution as a granulation medium. For example, it can be carried out by any means such as rolling granulation, extrusion granulation, spray granulation, tableting granulation, and fluidization granulation. 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. As the water-soluble polymer binder, starch, cyanoethylated starch, carboxymethyl starch, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, vinyl ether maleic acid copolymer, sodium alginate, sodium lignin sulfonate, gum albia, gum tragan, etc. are used. be able to. 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 shell-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 described 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, granules with a core-shell structure are prepared, which are air-dried and then calcined at a temperature 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. 4 showing the cross-sectional structure of the granular activated carbon used in the present invention, the granular activated carbon 14 consists of a granular activated carbon body 15 and a synthetic resin latex coating 16 formed on its surface. This coating 16
Since it is formed from synthetic resin latex, it has a remarkable feature that it does not substantially reduce its adsorption to organic solvents, and furthermore, it significantly suppresses dust generation. It will be immediately clear from the results of the example. 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 16 is derived from synthetic resin latex, It is a film or netting that has countless pores, and although it allows organic solvent vapor to pass through, it acts as a film sufficient to prevent the activated carbon from being worn out, and this film can also be used as a cushion 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. Generally, 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 in terms of powder resistance, Spherical ones 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, methacrylnitrile, 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 methacrylic esters. (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. If the amount of latex used is less than 1% by weight, the effect of reducing fineness will be small;
When the amount is more than % by weight, the effect of reducing fineness is large, but the gas adsorption performance decreases. 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 The granular zeolite of the present invention has the property of having a significantly large amount of water adsorption even when the humidity is extremely low, and furthermore, it has the property of having a significantly large amount of water adsorption even when the humidity is extremely low _. ) has the characteristic that the amount of moisture adsorbed is constant, with almost no relation to
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 Moreover, granular activated carbon
It has the property of selectively adsorbing organic solvents regardless of the presence of water vapor. Thus, in accordance with the present invention, the combination of granular zeolite and granular activated carbon provides the most effective adsorption of vapor components within double glazing to prevent condensation on the glass despite significant changes in temperature. Fogging 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. The present invention is characterized in that the granular zeolite and the granular activated carbon are located in separate accommodation spaces within the spacer. That is, for example, granular activated carbon is housed in a spacer serving as the lower side of the double-glazed glass, and granular zeolite is housed in a spacer serving as the top or side side. According to this aspect, segregation between the granular zeolite and the granular activated carbon and the accompanying compositional heterogeneity can be prevented, and abrasion and powdering caused by mixing different materials can also be completely prevented. In addition to the above-mentioned essential components, the adsorbent for double-glazing used in the present invention can contain other adsorbents as desired. In one embodiment of the present invention, based on the total amount of granular zeolite and granular activated carbon, 70% by weight or less, especially
When 10 to 60% by weight of granular alumina-silica gel is blended, moisture adsorption under high humidity conditions is further improved, and a double-glazed glass assembly with even better adsorption properties can be obtained. Such granular alumina-silica gel is known per se, for example,
Those described in No. 38-17002, No. 40-16347 and No. 47-8446 are preferably used. In the present invention, the above-mentioned combined adsorbent is generally used in an amount of 20 to 300 g per unit area (m ² ) of the double-glazed glass, although it also differs depending on the spacing between the double-glazed windows.
In particular, it is preferable to use it in an amount of 40 to 200 g. All the sealants conventionally used for this type of double-glazed glass can be used as sealants, such as two-component sealants using polysulfide rubber, one-component elastic sealants using butyl rubber, and urethane. Any one-component type elastic sealant using rubber can be used, and according to the present invention, even if these sealants are organic solvent type, excellent dew condensation prevention ability can be obtained. 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. The 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.

[Table] Next, 60 kg of the core produced by the above method was placed in a rolling granulator, and while rolling it, 3 kg of powder S-1 shown in Table 1 was added for coating the shell part.
Spherical zeolite with a spherical diameter of 0.3 to 3.0 mm was obtained by surface coating. Products coated with powders S-2 and S-3 were obtained in a similar manner. Incidentally, spherical zeolite with a spherical diameter of 0.5 to 3.0 mm was produced without coating. This is designated as S-4. The thus obtained wet spherical zeolite was air-dried (naturally dried).
Then, after drying for 3 hours in an atmosphere of 100 to 150℃
It was baked at 550±30°C for 3 hours. The compressive strength, abrasion resistance, packing density, equilibrium water adsorption amount, water adsorption rate, and pulverization rate of the wear-resistant zeolite thus obtained were measured by the following methods. The results are shown in Table 2. 1 Compressive strength: The compressive breaking strength of 20 samples was measured using a Kiya type hardness tester (maximum measurement amount: 10 kg) (manufactured by Kiya Seisakusho), and was expressed as the average value of 18 samples excluding the maximum and minimum values. 2. Abrasion rate: 40g of sample that was adsorbed to saturation in a 150ml glass container and dried at 150℃ for 3 hours.
Add 100 ml of water to the sample, attach it to a paint conditioner (manufactured by Red Devil Co., Ltd.), and shake for 30 minutes. Remove the powder adhering to the sample, and incubate at 150℃ for 3 minutes.
The weight of the dried sample was measured, and the wear rate (%) was determined from the following formula. Abrasion rate (%) = (1 - weight after abrasion test/sample) x 100 3 Packing density: Place 200g of the sample in a 500ml measuring cylinder and tap the container lightly on a rubber plate to find the volume at which the sample volume no longer changes. (V()) was read and the packing density was determined from the following formula. Packing density (g/) = 200/V 4 Equilibrium moisture adsorption amount: After placing 0.15 g of the sample in a quartz microbalance moisture adsorption tester and degassing it at 200℃ for 2 hours, the equilibrium moisture content at 20℃ relative humidity of 75% The amount of adsorption was determined. Equilibrium water adsorption amount (%) = adsorbed water amount (g) / sample (g)
×100 5 Moisture adsorption rate: 0.15 g of sample with particle size of 1.5 to 1.6 mm
was placed in a quartz microbalance moisture adsorption tester and degassed at 200℃ for 2 hours.The amount of moisture adsorption (mg) at 20℃ relative humidity 20% was measured every minute, and the horizontal axis shows time (unit: minute). ) The water adsorption amount was plotted on the vertical axis, a water adsorption curve was drawn, and the slope of the straight line connecting the water adsorption amount and the origin at an adsorption time of 10 minutes was determined and defined as the water adsorption rate. The water adsorption rate was expressed in units of (g/100g sample/min). 6 Powderization rate measurement method Sample 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 x 100 Sample container: Standard sieve (JIS Z-8801) (diameter 15
cm) Stack 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: JIS R6002 (1978) Number of rotations: 290 times/min Number of impacts: 156 times/min

[Table] From Table 2, 4A type spherical zeolite S-3 produced in Comparative Example is inferior in water adsorption amount and moisture adsorption rate, and Comparative Example S-4 is similarly inferior in powdering rate, so it is difficult to use as an adsorbent for this purpose. It is inappropriate as such. Reference Example 2 As a core part of spherical zeolite, 60 parts by weight of 4A type synthetic zeolite dry powder and 40 parts by weight of kaolin dry powder were sufficiently mixed in a V-shaped mixer to produce a mixed powder of synthetic zeolite and kaolin. Reference Example 1 The mixed powder obtained here was processed using a rolling granulator.
A core was created and molded in the same manner as above to produce a spherical zeolite core. 60 kg of this wet granular zeolite core was placed in a rolling granulator, and while rolling it, 6 kg of powder made by thoroughly mixing 50 parts by weight of kaolin and 50 parts by weight of synthetic zeolite for shell was added, and the same method as in Reference Example 1 was carried out. A granulated product with a spherical diameter of 1.5 to 3.0 mm was obtained by coating. The product obtained here is referred to as S-5. Next, as a comparative example, as a core part of spherical zeolite, 50 parts by weight of 4A type synthetic zeolite dry powder and 50 parts by weight of kaolin dry powder were sufficiently mixed in a V-shaped mixer to produce a mixed powder of synthetic zeolite and kaolin. did. The mixed powder thus obtained was molded into cores using a rolling granulator in the same manner as in Reference Example 1 to produce a spherical zeolite core. 60 kg of this wet granular zeolite core was placed in a rolling granulator, and while rolling it, 6 kg of powder made by thoroughly mixing 60 parts by weight of kaolin and 40 parts by weight of synthetic zeolite for shelling was added, and the same method as in Reference Example 1 was carried out. A granulated product with a spherical diameter of 1.5 to 3.0 mm was obtained by coating. The product obtained here is referred to as S-6. Next, both S-5 and S-6 were dried and fired in the same manner as in Reference Example 1 to obtain products. The granular zeolite obtained here has compressive strength, abrasion resistance, packing density,
The equilibrium water adsorption amount, water adsorption rate, and powdering rate were measured and the results are shown in Table 3.

[Table] From Table 3, the 4A type spherical zeolite S-6 produced in the comparative example has an excellent powdering rate, but is inferior in water adsorption amount and water adsorption rate, and is therefore unsuitable as an adsorbent for this purpose. Reference Example 3 As a core part of spherical zeolite, 90 parts by weight of 4A type synthetic zeolite dry powder and 10 parts by weight of attapulgite dry powder were sufficiently mixed in a V-shaped mixer to produce a mixed powder of synthetic zeolite and attapulgite. The mixed powder thus obtained was molded into cores using a rolling granulator in the same manner as in Reference Example 1 to produce a spherical zeolite core. 60 kg of this wet granular zeolite core was placed in a rolling granulator, and while rolling it, 6 kg of powder S-7 shown in Table 4 for shells was added and coated in the same manner as in Reference Example 1 to form spheres. Diameter 1.5~3.0
mm granular zeolite was obtained. Next, as a comparative example, powder S-8 shown in Table 4
Granular zeolite was also obtained in the same manner.

【table】

[Table] Next, as a comparative example, as a core part of granular zeolite, 95 parts by weight of 4A type synthetic zeolite dry powder and 5 parts by weight of attapulgite earth dry powder were thoroughly mixed in a V-shaped mixer. A mixed powder was produced. The mixed powder thus obtained was molded into cores using a rolling granulator in the same manner as in Reference Example 1 to produce a spherical zeolite core. 60 kg of this wet granular zeolite core was placed in a rolling granulator, and while rolling, 6 kg of powder S-9 shown in Table 4 for shells was added and coated in the same manner as in Reference Example 1 to form spheres. Diameter 1.5~3.0
mm spherical zeolite was obtained. The S− obtained here
7. For S-8 and S-9, pressure resistance, abrasion resistance,
The packing density, equilibrium water adsorption amount, water adsorption rate, and powdering rate were measured and the results are shown in Table 5 below.

[Table] From Table 4, 4A type spherical zeolites S-8 and S-9 produced in comparative examples have poor powderization efficiency and are therefore unsuitable as adsorbents for this purpose. Reference example 4 Spherical activated carbon 100 made by coal-based steam activation method with a BET specific surface area of 1080 m ² /g and a particle size of 1.68 to 0.5 mm.
Synthetic rubber latex (SBR styrene-
Butadiene copolymer (carboxyl group-modified solid content concentration: 47% by weight) was diluted with water to give a solid content concentration of 10% by weight. 10, 25, and 50ml each were mixed with activated carbon using a hand sprayer. After spraying while
Low-powder treated charcoal S-10, S-11, S-12 dried in an air bath dryer at 100℃ and with different amounts of latex used.
I got it. Next, as a comparative example, 5 ml of the same synthetic rubber latex diluted solution was added to 100 g of the above activated carbon in the same manner as above to obtain low powder treated carbon S-13 having a different amount of latex used. A performance test was conducted on the low pulverization coal thus obtained 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 305mmH (stainless steel cylinder with internal volume of 150ml) Sample filling amount 50ml Rotation speed 20RPM Rotation time 30min Calculation method for powdering rate Powdering rate (%) = sample weighed amount - after measurement Sample weight/sample weighed amount x 100 The samples before and after measurement were sieved for 5 minutes using a rotary tap machine using a 32-mesh sieve, and the sample remained on the sieve. 2 Equilibrium adsorption amount of acetone 37.5 at 25℃ according to JIS-K-1474 method
The equilibrium adsorption amount of g/m ³ acetone gas was measured. Measurement result

[Table] The low-pulverization treated charcoal produced in the comparative example has similarly excellent organic gas adsorption performance as indicated by the equilibrium adsorption amount of acetone, but its abrasion resistance strength as indicated by the pulverization rate is low, which is not suitable for this purpose. Not suitable as an adsorbent. Reference example 5 Synthetic rubber latex (NBR (butadiene-acrylonitrile copolymer-carboxyl group modified ^, solid 75 ml and 100 ml of each liquid was diluted with water to give a solid concentration of 20 wt. %) and sprayed with activated carbon while stirring using a hand sprayer, and then dried in an air bath at 100°C. It was dried in a pot to obtain low-powder treated carbon S-14 and S-15 with different amounts of latex used. Next, as a comparative example, the same synthetic rubber latex as above was diluted with water to 100 g of the same activated carbon, and the solid content was 83ml of the liquid prepared to a concentration of 30% by weight was processed in the same manner as above to produce low powder treated charcoal S-16 with different amounts of latex used.
I got it. A performance test was conducted on the low pulverization coal thus obtained 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 305mmH (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 weighing Amount - Weight of sample after measurement/Amount of sample weighed x 100 Both samples before and after measurement are samples that were sieved for 5 minutes using a rotorp machine using a 32-mesh sieve and remained on the sieve. 2 Equilibrium adsorption amount of acetone 37.5 at 25℃ according to JIS-K-1474 method
The equilibrium adsorption amount of g/m ³ acetone gas was measured. Measurement result

[Table] The low-pulverization treated charcoal produced in the comparative example has similarly excellent abrasion resistance strength as indicated by the pulverization rate, but its organic gas adsorption performance as indicated by the acetone equilibrium adsorption amount is low, making it difficult to use as an adsorbent for this purpose. It is inappropriate as such. Reference Example 6 4A type spherical zeolite S- produced in Reference Example 1
Low powder spherical activated carbon S- manufactured in 2 and Reference Example 4
12 Moisture adsorption isotherms are shown in Figure 5. Furthermore, the adsorption isotherms of MEK (methyl ethyl ketone) and m-xylene, which are used as a solvent for a sealant for double-glazed glass, are shown in FIGS. 6 and 7, respectively, with relative humidity maintained at 43% and 20%. As comparative examples, 4A type zeolite manufactured by a certain domestic company and silica gel manufactured by a certain domestic company were similarly measured and shown in each figure. The above performance was measured by the following test method. 6-1 Moisture adsorption isotherm The equilibrium moisture adsorption amount at each relative humidity was determined using the quartz microbalance moisture adsorption tester of Reference Example 1. Reference Example 6-2 Adsorption isotherm of MEK (methyl ethyl ketone) and m-xylene Measurement was carried out under the following conditions using the gas circulation adsorption test apparatus shown in FIG. Measurement operation: Connect the gas circulation system shown in Figure 8 to the bypass F flow path by operating the gas flow switching knob G, and connect the sample column D to the bypass F flow path.
Precisely weigh about 2 g of sample, fill it, and set it in the device. While operating the diaphragm pump B and circulating the air at a constant humidity in the gas holder A, inject a certain amount of MEK or m-xylene from the gas inlet E, and while continuing to circulate the gas, inject a certain amount of MEK or m-xylene into the gas sampling port E. Sample the gas and analyze the gas concentration using gas chromatography. Once the gas concentration has stabilized, operate the gas flow path switching knob G to switch the gas flow path to the sample column D side, sample the gas at regular intervals, and measure the change in gas concentration over time. Once the gas concentration in gas holder A has stabilized and reached equilibrium, operate the gas flow switching knob G to set the bypass F flow path, and repeat the steps ~ to reach the equilibrium point of the gas concentration. Measure. The measurement results are converted to equilibrium adsorption lines using the following method. In the measurement results of changes in gas concentration over time, the concentration at the time when the gas concentration stabilizes is taken as the equilibrium concentration, and the amount of MEK or m-xylene injected to reach that concentration, and the amount of MEK or m-xylene remaining in the system after measurement. Calculate the equilibrium adsorption amount using the following formula from the amount of sample used for measurement and plot it at each corresponding equilibrium concentration to obtain an equilibrium adsorption line. Q=VC ₀ (1-Cs/C ₀ )/W where Q: Equilibrium adsorption amount (mg/g-adsorbent) V: Total gas volume () C ₀ : Initial gas concentration (mg/) Cs: Equilibrium Gas concentration (mg/) W: Sample amount (g) Example 1 Manufactured in Reference Example 1 as an adsorbent on the aluminum spacer for double-glazed glass shown in Figures 1 and 2 in a room at a temperature of 25°C and relative humidity of 50%. Particle size 1.68~0.84mm
4A type spherical zeolite S-2 and low powder spherical activated carbon S-12 with a particle size of 1.68 to 0.50 mm produced in Reference Example 4.
A total of 15 g of each was filled individually at a mixing ratio of 80:20, and the corners of the spacers were connected with corner keys to create a double-glazed window frame. next,
The glass adhesive part of the spacer was thoroughly cleaned with a piece of cloth soaked in toluene, and after drying, double-sided adhesive tape was adhered, and a 3 mm thick glass plate was adhered thereon. Next, to seal the glass plate and the spacer, a polysulfide-based (thiokol) liquid polymer and a vulcanizing agent are used as a sealant.
Mix thoroughly at a ratio of 100:10, fill the space between the spacer and the glass using a sealing gun, and leave it indoors for 24 hours to harden the sealant. was created. The double-glazed glass produced in this way is JIS R-3209
(1979) 8.4, the dew point was measured under the following conditions. Dew point measurement conditions Initial dew point: Dew point measurement after 12 days at room temperature of 20°C High temperature and high humidity resistance test: JIS R-3209 8.5.
Measurement of dew point after 14 days of exposure under condition 2. As a result of the measurement, the initial dew point was -60.0°C and the dew point in the high temperature and high humidity resistance test was -68.0°C. Example 2 The 4A type spherical zeolite S-2 with a particle size of 1.68 to 0.84 mm produced in Reference Example 1 and the particle diameter produced in Reference Example 4 were used as adsorbents on the aluminum spacer for double-glazed glass shown in Figures 1 and 2. A total of 10 g of low-powder spherical activated carbon S-12 of 1.68 to 0.50 mm was filled individually at a mixing ratio of 40:60, and vertically packed in the same manner as in Example 1.
A double-glazed glass measuring 30 cm long, 30 cm wide, and 12 mm thick was prepared, and its dew point was measured in the same manner as in Example 1. As a result of the measurement, the initial dew point was -48.0°C, and the dew point of the high temperature and high humidity resistance test was -52.5°C. Comparative Example 1 15 g of the 4A type spherical zeolite S-2 with a particle size of 1.68 to 0.84 mm produced in Reference Example 1 was filled into a spacer for double-glazed glass, and the same method as in Example 1 was carried out to form a spacer with a length of 30 mm.
A double-glazed glass with a width of 30 cm and a thickness of 12 mm was prepared, and the dew point was measured in the same manner as in Example 1. As a result of the measurement, the initial dew point is -32.0℃ The dew point of the high humidity resistance test is -
It was 21.0℃. Comparative Example 2 10.0 g of low-powder spherical activated carbon S-12 with a particle size of 1.68 to 0.50 mm produced in Reference Example 4 was filled into a spacer for double-glazed glass, and the same method as in Example 1 was carried out to form a spacer with a length of 30 mm.
A double-glazed glass measuring 30 cm wide and 12 mm thick was prepared, and its dew point was measured in the same manner as in Example 1. As a result of the measurement, the initial dew point was -23.0°C, and the dew point in the high humidity resistance test was -10.0°C. Comparative Example 3 Particle size commercially available as adsorbent for double glazing
In the same manner as in Example 1, 15 g of a mixed adsorbent of 50% by weight of 4A type spherical zeolite with a particle size of 1.68 to 0.84 mm and 50% by weight of spherical silica gel with a particle size of 1.68 to 0.84 mm was filled into a spacer for double-glazed glass, and the spacer was 30 cm long. Width 30cm, thickness 12mm
A double-glazed glass was prepared, and the dew point was measured in the same manner as in Example 1. As a result of the measurement, the initial dew point was -42.0°C, and the dew point of the high humidity resistance test was -33.0°C.

[Brief explanation of drawings]

FIGS. 1 and 2 are a three-dimensional view and a cross-sectional view of the double-glazed glass used in Example 1, and the numbers in the drawings indicate dimensions (unit: mm). FIG. 3 is a diagram showing the cross-sectional structure of granular zeolite used in the present invention, and FIG. 4 is a diagram showing the cross-sectional structure of granular activated carbon used in the present invention. Figure 5 is the moisture adsorption isotherm of Reference Example 6, Figure 6 is the MEK adsorption isotherm of Reference Example 6, and Figure 7 is the m of Reference Example 6.
-Xylene adsorption isotherm, FIG. 8 shows the gas circulation type adsorption test apparatus shown in Reference Example 6. Reference symbols 1a and 1b are glass plates, 2 is a spacer, 3 is double-sided adhesive tape, 4 is a space, 5 is a sealant, 6 is an adsorbent, 7 is a spacer opening,
11 is granular zeolite, 12 is core, 13 is shell, 14 is granular activated carbon, 15 is activated carbon body, 16
22 is a synthetic resin latex coating, 22 is a low powder spherical activated carbon of the present invention (Reference Example 4S-12), 23 is a spherical silica gel manufactured by a certain domestic company, 24 is 4A type spherical zeolite manufactured by a certain domestic company, A is a gas holder, and B is a diaphragm. Pump, C is flow meter, D is sample column (φ37.5
mm glass column), E is the glass injection hole and sampling hole, F is the bypass, G is the gas flow path switching hole, H is the potassium acetate saturated solution (RH20%)
Alternatively, a saturated solution of potassium carbonate (RH43%) is shown.

Claims (1)

[Scope of Claims] 1. A double-glazed glass assembly comprising a spacer member containing an adsorbent inside located on at least one side of the periphery of a plurality of glass plates, and a peripheral portion sealed with a sealant, comprising: A core consisting of a synthetic zeolite-clay binder mixture in which the agent contains synthetic zeolite in an amount greater than the average content, and a synthetic zeolite-clay binder mixture containing a clay binder in an amount greater than the average content. 1 per activated carbon.
A complex comprising a combination of granular activated carbon having a synthetic resin latex coating agent of 20% by weight on its surface, and wherein the granular zeolite and the granular activated carbon are located in separate storage chamber spaces within the spacer member. Layer glass assembly. 2 What are the granular synthetic zeolite and granular activated carbon?
An assembly according to claim 1, wherein the weight ratio is between 95:5 and 30:70. 3. An assembly according to claim 1 or 2, further comprising granular alumina-silica gel as an adsorbent in an amount of not more than 70% by weight based on the total amount of granular zeolite and granular activated carbon. 4. An assembly according to claim ¹ , wherein the adsorbent is present in an amount of 20 to 300 g per square meter of double glazing. 5. The assembly of claim 1, wherein the core and shell of the granular zeolite are present in a weight ratio of 99:1 to 80:20. 6 The core in 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. An assembly according to claim 1, characterized in that it contains: 7 Synthetic zeolite in granular zeolite is A
The assembly according to claim 1, which is a type zeolite, type X zeolite, type Y zeolite or synthetic mordenite. 8. The assembly 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. 9 The active body in granular activated carbon is 500 to 500
An assembly according to claim 1, having a BET specific surface area of 2000 m ² /g. 10. An assembly according to claim 1, wherein the coating of granular activated carbon is applied in the form of an aqueous emulsion.