JP5410893B2 - Compact - Google Patents

Description

  The present invention relates to a molded body containing particles having an adsorption function. In detail, it is related with the molded object provided with the adsorption | suction performance which can be utilized suitably as various adsorption | suction means utilized for an air conditioner, a separation refinement | purification apparatus, etc.

  Particles having an adsorption function such as zeolite (also called “adsorptive particles”) are used as adsorbents for moisture and other components in gas separation and purification, filters, adsorption heat pumps, catalysts, humidity control, deodorization, etc. ing. Examples of the adsorbent particles that absorb and desorb moisture include zeolite, silica gel, activated carbon, and mesoporous silica. Among them, zeolite that can easily adsorb water vapor can control adsorption / desorption characteristics by controlling pore diameter and electric charge, and is expected to be used for adsorption heat pumps, desiccant air conditioning, and the like.

  In these applications, in order to enhance the adsorption function, a substance containing adsorbent particles is often used after being formed into a honeycomb shape which is a cell aggregate. For example, a rotor-type adsorbing element (digican rotor) formed by processing adsorbent particles into a thin sheet into a honeycomb-shaped hollow structure is known as a moisture absorber such as an air conditioner. Further, a desiccant rotor having a honeycomb structure carrying zeolite powder is also known as a moisture absorber such as an air conditioner.

  Examples of methods for producing a honeycomb formed body or a desiccant rotor using adsorbent particles in this way include an impregnation method and an extrusion method.

  With the impregnation method, heat-resistant paper such as inorganic fiber paper is processed into a corrugated corrugated cardboard, and bonded to produce a honeycomb, which is impregnated with a slurry of adsorbent particles such as zeolite, It is a method of fixing. The impregnation method is a common production method for desiccant rotors, but there are problems such as the zeolite powder falling off from the molded body, the high loading of the zeolite being difficult, and uneven fixing. . In addition, since the impregnation and drying steps are repeated, there is a problem that productivity is low.

  On the other hand, the extrusion method is a method in which a desiccant rotor is manufactured by extruding a composition containing adsorbent particles in a honeycomb shape from a die using an extruder and combining the extruded honeycomb-shaped adsorbing elements. In this extrusion method, the cell density, cell wall thickness, and cell shape of the honeycomb can be controlled by the design of the die, so that the obtained extruded honeycomb has a high degree of freedom. In addition, since the honeycomb obtained by the extrusion method does not require a support such as paper, the adsorbent particles can be highly loaded, and there is little unevenness in sticking amount and powder falling. Furthermore, since it can be produced continuously, there is an advantage that it is excellent in productivity. However, the honeycomb molded body obtained by the extrusion method has a smooth honeycomb cell wall, and in order to increase the adsorption rate, it is necessary to make the honeycomb cell wall thinner or porous. When the thickness is reduced or the porosity is increased, the strength of the honeycomb formed body is lowered. In other words, there is a trade-off between reducing the thickness or porosity of the molded body in order to increase the adsorption speed and maintaining the strength of the molded body, and it was a difficult solution to increase both. .

  By the way, the adsorptive particles represented by zeolite are often not self-sintering and cannot be kept in their own shape even when fired. Therefore, the adsorbent particles can be molded by adding a binder. The binder used at this time is an important component that affects the strength of the molded body. Therefore, various binders have been proposed for the purpose of improving the strength of the molded body.

  For example, silica sol can be given as a typical inorganic binder. Patent Document 1 discloses an adsorptive honeycomb-like ceramic body obtained by blending zeolite powder with sepiolite fibers and colloidal silica, extrusion-molding into a honeycomb shape, and firing.

  In Patent Document 2, tetramethyl orthosilicate as a binder and hydroxyethyl cellulose as a plasticizer are added to a pentasil-based zeolite, and the resulting mixture is kneaded and then molded into a strand shape. A method for producing a molded body by drying the product and baking it at a temperature of 400 ° C. to 800 ° C. for 2 hours is disclosed.

  Patent Document 3 discloses a zeolite molded body using an oligomer of an alkylalkoxysilane as a binder. Since the liquid alkoxysilane oligomer is used, the dispersibility is good, and the compression strength of the fired molded body can be higher than that of the molded body using silica sol as a binder.

  Patent Document 4 discloses a zeolite molded body using a silanol group-containing polysiloxane oligomer having a nitrogen-containing group as a binder. Since such a binder is water-soluble by a nitrogen-containing group, it has excellent dispersibility in aqueous honeycomb extrusion, and forms a strong and continuous binder phase after firing. Therefore, the fired body exhibits excellent compressive strength.

Japanese Patent No. 2627466 German Patent Application Publication No. 3231498 Specification Japanese translation of PCT publication No. 2002-509788 Japanese Patent No. 4131152

  As disclosed in Patent Document 1, a zeolitic honeycomb having a silica sol as a binder is fired at 400 to 700 ° C. for at least 1 hour. However, since the silica sol binder of the formed body is colloidal particles, When stress is applied, stress concentration at the adhesion interface of colloidal particles occurs, so that only a brittle shaped body can be obtained. For this reason, it is very weak against deformation such as bending, and it has been difficult to make the honeycomb cell walls thinner or porous. Furthermore, since the firing temperature is high and the time required for heating and cooling the furnace is increased, there is a problem that the manufacturing cost is high.

In any of the zeolite-based honeycombs disclosed in Patent Documents 2 to 4, when the pore formation material is not used, the binder phase covers the surface of the adsorptive particles. There was a problem that decreased. In addition, when the pore formation is performed, there is a problem that the continuity of the binder phase is lost and the molded body becomes brittle.
Further, in Patent Document 2, since tetramethyl orthosilicate has a small molecule, there is a problem that the pores are blocked by depositing inside the zeolite. In Patent Document 3, alcohol is dissolved by hydrolysis of the alkoxysilane oligomer. There is also a problem that cracks are likely to occur due to the large amount of by-products.

In this way, even if the conventional technology is examined, the technology that can maintain the strength of the molded body while reducing the thickness and the porosity of the molded body, and can maintain the adsorption performance of the adsorbent particles. Did not exist.
Accordingly, an object of the present invention relates to a molded article containing adsorptive particles, and can maintain the strength of the molded article while reducing the thickness or the porosity of the molded article, while maintaining the adsorption performance of the adsorbent particles. An object of the present invention is to provide a new molded body that can be used.

  The present invention is a molded article comprising adsorbent particles and a binder comprising a curable silicone composition, wherein the binder has rubber elasticity at room temperature, and the content of the adsorbent particles is Provided is a molded body characterized in that it is 60 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total amount of adsorbent particles and binder, and is made porous by a pore former. It is.

  In the molded article of the present invention, by using a predetermined polyorganosiloxane, that is, silicone, as the main component of the binder, the molded article can be made thinner and porous while maintaining the adsorption performance. In particular, by using a curable silicone composition that exhibits rubber elasticity by being crosslinked and cured, sufficient strength can be maintained even if the composition is made porous. That is, while maintaining the strength of the molded body, the adsorption rate can be increased by making the pores porous. Therefore, the molded object of this invention can be utilized suitably for a desiccant rotor, a filter, an air conditioner, a gas separation refinement | purification apparatus, a fixed catalyst, a deodorizing apparatus, a heat exchanger etc., for example.

It is a figure for demonstrating the microscopic state which the binder has couple | bonded between adsorptive particles in an example of the molded object of this invention. It is a chart of the storage elastic modulus of the binder cured product when the binder alone used in Example 1 is cured and the dynamic viscoelasticity is measured at a vibration frequency of 10 Hz. It is a load-stroke correlation curve figure in the 3 point | piece bending test of the strip-shaped molded object obtained by each Example and the comparative example.

  Examples of embodiments of the present invention will be described below. However, the scope of the present invention is not limited to the embodiments described below.

<Adsorbent particles>
There are no particular restrictions on the adsorptive particles used in the molded article, and conventionally known particles having an adsorption function such as zeolite, silica gel, activated carbon, ion exchange resin, and polymer adsorbent can be used. From the viewpoint, the adsorptive particles are preferably one type or two or more types selected from the group consisting of zeolite, silica gel, mesoporous silica, and activated carbon.
For example, in applications where water vapor is adsorbed / desorbed, the adsorbent particles are preferably zeolite, and among them, a variety of particles that are easy to desorb water vapor at low temperatures have been found, so the group consisting of aluminosilicates and aluminophosphates. It is preferable that it is a zeolite consisting of one kind of zeolite selected from the above or a combination of two or more kinds.

(Zeolite)
Zeolite is a general term for aluminosilicates with fine pores in the crystals. The skeleton of zeolite is formed by three-dimensionally combining the structures of Si-O-Al-O-Si, and the skeleton has molecular-level pores. Various molecules such as water and organic molecules Can be taken into the skeleton and adsorbed.

  The zeolite used in the molded article may be either natural zeolite or synthetic zeolite, but synthetic zeolite is preferable in that the adsorption performance can be adjusted appropriately.

  Natural zeolite can be classified by crystal structure, for example, tachabasite, clinoptilolite, erionite, mordenite, hydrotalcite and the like.

  The synthetic zeolite is not particularly limited as long as it is effective in the molded body, but is selected from the group consisting of aluminosilicates and aluminophosphates from the viewpoint of the regeneration temperature and adsorption characteristics of the zeolite. It is preferable to be a zeolite of a kind or a combination of two or more kinds.

  Examples of the aluminosilicate zeolite include MFI, MEL, MTW, * BEA, MWW, CHA, DDR, RHO, LEV, and the like, when expressed by a zeolite structure code defined by the International Zeolite Society.

The silica alumina ratio (SiO ₂ / Al ₂ O ₃ molar ratio) is 5.5 or more, preferably 6 or more, more preferably 7 or more.

  Among the zeolites, crystalline aluminophosphates (hereinafter sometimes abbreviated as ALPOs) containing at least Al and P in the skeleton, which can more easily desorb water vapor at a low temperature, are more preferable.

  In the crystalline aluminophosphate, atoms constituting the skeletal structure are aluminum and phosphorus, and a part thereof may be substituted with other atoms. Among them, I) aluminum is a heteroatom (Me1: where Me1 belongs to the 3rd or 4th period of the periodic table, elements 2A, 7A, 8, 1B, 2B, 3B (except Al) A partially substituted Me-aluminophosphate, II) phosphorus is a heteroatom (Me2: where Me2 is a Group 4B element belonging to the third or fourth period of the periodic table) ) Or Me-aluminophosphate in which both aluminum and phosphorus are substituted with heteroatoms (Me1 and Me2 respectively) are preferred from the standpoint of adsorption properties.

In such crystalline aluminophosphate, the constituent ratio (molar ratio) of Me, Al and P constituting the skeleton structure is preferably a molar ratio of the following formula 1-1-3-1, The following formula 1-2-3-2 is particularly preferable.
If x is not less than the lower limit of the following range, the amount of adsorption in the region where the pressure of the adsorbate is low does not become small, and synthesis is relatively easy. On the other hand, if x is less than or equal to the upper limit of the above range, impurities tend not to be mixed during synthesis. If y and z are within the above ranges, synthesis is easy.

0 ≦ x ≦ 0.3 Formula 1-1
(X represents the molar ratio of Me to the total of Me, Al, and P)
0.2 ≦ y ≦ 0.6 Formula 2-1
(Y represents the molar ratio of Al to the total of Me, Al, and P)
0.3 ≦ z ≦ 0.6 Formula 3-1
(Z represents the molar ratio of P to the sum of Me, Al, and P)
0.01 ≦ x ≦ 0.3 Formula 1-2
(X represents the molar ratio of Me to the total of Me, Al, and P)
0.3 ≦ y ≦ 0.5 Formula 2-2
(Y represents the molar ratio of Al to the total of Me, Al, and P)
0.4 ≦ z ≦ 0.5 Formula 3-2
(Z represents the molar ratio of P to the sum of Me, Al, and P)

  Me may be contained alone or in combination of two or more. Preferable Me (Me1, Me2) is an element belonging to the third and fourth periods of the periodic table.

Me1 preferably has an ionic radius of 3 to 0.8 nm in a divalent state, and more preferably has an ionic radius of 0.4 to 7 nm in a divalent and tetracoordinate state. Among these, at least one element selected from Fe, Co, Mg, and Zn is preferable from the viewpoint of ease of synthesis and adsorption characteristics, and Fe is particularly preferable.
Me2 is a Group 4B element belonging to the third or fourth period of the periodic table, and is preferably Si.

Further, aluminophosphate compounds used in the present molded product, the framework density (FD) of preferably at 13T / nm ³ or more 20T / nm ³ or less, particularly 13.5T / nm ³ or more more preferably, even more preferably at inter alia 14T / nm ³ or more, and it is more preferably 19T / nm ³ or less.
Here, T / nm ³ means a T atom existing per unit volume nm ³ (the number of elements constituting a skeleton other than oxygen per 1 nm ^{3 of} zeolite), and is a unit indicating framework density: FD. .
If the FD of the aluminophosphate is not less than the lower limit of the above range, the structure is stabilized and durability can be maintained, while if it is not more than the upper limit of the above range, the adsorption capacity can be maintained and the adsorption can be maintained. It exhibits its function as a suitable material.

  The structure of the aluminophosphate used in the molded body is a code defined by the International Zeolite Society, AEI, AEL, AET, AFI, AFN, AFR, AFS, AFT, AFX, ATO, ATS, CHA, Among them, ERI, LEV, and VFI are mentioned, and among them, from the viewpoint of adsorption characteristics and durability, any one selected from AEI, AEL, AFI, CHA, and LEV is preferable, and AFI and CHA are particularly preferable.

Examples of such aluminophosphates include SAPO-34 (CHA type silica aluminophosphate), FAPO-5 (AFI type iron aluminophosphate) and ALPO-5 (AFI type aluminophosphate).
The ALPOs can be used alone or in combination of two or more.

  The particle size of zeolite is as small as possible from the viewpoint of adsorption efficiency, specifically, from the viewpoint of enhancing the adsorption / desorption ability by promoting the diffusion of adsorbate vapor and water vapor, and the viewpoint of improving the adhesion strength of the adsorbent particles. However, if the particle size is too small, the periphery of the adsorptive particles is likely to be covered with the binder and the adsorption performance is lowered. Specifically, the average particle size (D50) is 0.3 μm to 10 μm. In particular, 0.5 μm to 8 μm, particularly 1 μm to 6 μm is preferable.

(silica gel)
There are two types of silica gel: A-type with a dense structure (surface area of about 700 m ² / g) and B-type with a gentle structure (surface area of about 450 m ² / g). Type A has a large surface area and is convenient for chemical adsorption, and is suitable for further reducing the humidity under low humidity conditions. On the other hand, the B-type has a rough structure, so that the capillary phenomenon is likely to work, and is suitable for absorbing a large amount of moisture under high humidity conditions. Both can be used according to the purpose.

(Mesoporous silica)
Examples of mesoporous silica include MCM41, MCM48, FSM16, SBA-1, HMS, MSU-1, MSU-3, SBA-12, SBA-15, SBA-16, and the like.

(Activated carbon)
The activated carbon is powdered activated carbon or granulated activated carbon having an average particle size of 0.1 μm to 300 μm, preferably 50 μm to 250 μm, and more preferably 100 μm to 200 μm.
The raw material and activation method of activated carbon are not particularly limited. After charcoalizing charcoal, palm nuts, sawdust, lignin, beef bone, lignite, cut charcoal, day charcoal, or coal, steam activation or chemical activation, etc. Can be used.

<Binder>
The binder used for the molded body, that is, the binder composed of the curable silicone composition needs to exhibit rubber elasticity at room temperature after curing.
By using a curable silicone composition that exhibits rubber elasticity upon curing as a binder, the binder phase formed by the binder can relieve physical stress, so it becomes porous with a pore former and the continuity of the binder phase. Even if this is lost, a tough molded body can be obtained. That is, by using the binder, it is possible to achieve both the adsorption capacity and strength of the molded body. Furthermore, since the binder after curing is a rubber elastic body at normal temperature, the external force applied to the molded body during processing such as cutting can be relaxed and distortion can be restored. Therefore, defects generated in the molded body can be reduced, and the manufacturing yield can be improved.

Rubber elasticity is caused by micro-Brownian motion of individual polymer chains, and is elasticity that occurs according to the second law of thermodynamics (entropy increasing law). In order to exhibit rubber elasticity, it is necessary that the molecules are long enough to be able to move freely and are reasonably bound to each other.
Since the reactive silicone that is the main component of the binder is not an oligomer but a polymer, the distance between cross-linking points is increased, and rubber elasticity can be exhibited.

Generally, the storage elastic modulus of the rubber elastic body is said to be 1 MPa to 10 MPa, and the storage elastic modulus at normal temperature after curing of the binder made of curable silicone used in the molded body is 1 MPa to 10 MPa.
In order to obtain a large amount of adsorptive particles and to obtain a tough molded body, the binder needs to have low elasticity, and among these ranges, the storage elastic modulus at room temperature is preferably 1 MPa to 3 MPa. .

  If the elastic rubber body is strained to a certain level, it exhibits the property of being restored to its original shape when the external force is removed. When the binder, which is a rubber elastic body as in the present invention, is finely dispersed in various shapes, it is difficult to accurately represent the distortion of the binder. Is defined as compressing to a size of 80% of the original size using calipers and restoring the size to 99% or more of the original size after 1 minute of unloading.

  Moreover, in the use which repeats adsorption / desorption, such as a desiccant rotor, from a viewpoint of preventing the defect by a heat cycle, it is calculated | required that a binder hardened | cured material shows rubber elasticity in a wide temperature range. The temperature range varies depending on the regeneration temperature of the adsorptive particles and the operating temperature at the time of use, but preferably has rubber elasticity at 0 to 150 ° C, particularly 0 to 200 ° C, particularly 0 to 250 ° C. It is preferable to have.

  Further, when the adsorbent particles are regenerated, heat resistance at the regeneration temperature is required, but sufficient heat resistance can be ensured because the binder is silicone.

  A commercially available curable silicone rubber can be used as a main component of the binder made of curable silicone used in the molded article. Silicone rubber is composed of siloxane bonds in the main chain and has an organic substituent in the side chain. Depending on the structure of the side chain, dimethyl silicone rubber (MQ), vinyl methyl silicone rubber (VMQ), phenyl methyl silicone rubber (PMQ), phenyl vinyl methyl silicone rubber (PVMQ), fluorosilicone rubber (FVMQ), and the like. Any silicone rubber may be sufficient as the silicone rubber used for this molded object.

Types of silicone rubber are classified into millable silicone rubber that becomes an elastic body by heat vulcanization after kneading a vulcanizing agent with a Banbury mixer or the like, and liquid silicone rubber that is liquid before vulcanization.
In this molded product, it is preferable to use liquid silicone rubber from the viewpoint that no special curing device is required.

  Millable silicone rubber is composed mainly of a linear polymer having a degree of polymerization of about 3000 to 10,000, and a silica-based reinforcing filler, wetting agent, and various additives. By adding a vulcanizing agent at the time of use, This is a type of rubber that is heat-cured.

On the other hand, the liquid silicone rubber is mainly composed of a linear polymer having a degree of polymerization of about 100 to 2,000, and like the millable silicone rubber, it contains various fillers and additives, but it is a low viscosity liquid and generally has a special curing. Does not require equipment. Further, it is a type of rubber that cures at room temperature or when heated.
Such liquid silicone rubbers are classified into a condensation type and an addition type depending on the curing type, and are one-component and two-component, respectively.

Condensation type liquid silicone rubber is a general term for what produces acetone, alcohol, and other condensation products upon curing, and is classified into one-pack type and two-pack type.
The one-pack type is cured from the surface by reacting with moisture in the air, and the two-pack type has a characteristic that the curing reaction proceeds simultaneously with mixing, and the surface and the inside are cured.
The condensation-type liquid silicone rubber exhibits a paste shape when uncured, and cures while releasing a small amount of condensate by reacting with moisture in the air. It adheres well to most materials and becomes a rubber elastic body after curing.

On the other hand, the addition-type liquid silicone rubber is cured by an addition reaction using a Pt compound (platinum compound) as a catalyst.
Both the one-pack type and the two-pack type are characterized by excellent deep-part curability. Further, by adjusting the amount of the platinum compound as a catalyst, it can be sufficiently cured even at room temperature.

  The binder used in the present invention is preferably not cured before molding. By using silicone rubber before curing, rubber elasticity can be imparted more effectively. Furthermore, if a curable silicone composition having many reactive substituents such as silanol groups is used as a binder, sufficient adhesion to the adsorbent particles can be secured, and interface separation between the binder phase and the adsorbent particles is difficult to occur. The strength of the molded body can be improved.

In the case of a silicone rubber that is cured by an addition reaction, it is preferable to use a condensation-type liquid silicone rubber because water hinders curing and it is difficult to use general aqueous molding.
Further, from the viewpoint of improving the adhesion with the adsorbent particles, the binder is preferably a condensation-type curable silicone composition having a reactive substituent such as a silanol group.
Condensation-type liquid silicone rubber produces acetone, alcohol, and other condensation products as a by-product during curing as described above. However, the amount is extremely small compared to silicate condensation, so the production line is made explosion-proof. Not only is there no need to worry about cracking of the molded body due to by-product gas.

  The binder used in the present invention is preferably a composition that cures at room temperature (RTV: Room Temperature Vulcanzing). This is because a curing device is unnecessary and manufacturing costs can be suppressed.

The condensation type room temperature curable silicone rubber has the property of being able to crosslink at room temperature and reacting with moisture in the air using the gas permeability of the silicone rubber to cure from the surface into a rubbery shape. As the cross-linking reaction, dealcohol condensation, deamine condensation, or the like is used.
In addition, among the condensation type room temperature curable silicone rubbers, those having a heat resistance of about 300 ° C. containing a heat resistance agent such as iron oxide and carbon black are commercially available.
By using these, excellent heat resistance can be imparted to the molded body. For example, trade name: KE-3418 manufactured by Shin-Etsu Chemical Co., Ltd., trade names: TSE3976-B, TSE3826, etc. manufactured by Momentive Performance Materials Japan GK.

  Further, although there is no particular limitation on the polarity of the binder, the binder is preferably hydrophobic from the viewpoint of exposing the particle surface of the adsorbent particles and improving the adsorption rate.

The binder used in the molded body is mainly composed of silicone, but can contain at least one filler or fiber as long as the function is not impaired. Examples of the filler include silica, iron oxide, alumina, titania, graphite, carbon black, and pigment. The heat resistance of a binder can be improved by adding a filler.
Moreover, this molded object can add at least 1 sort (s) among an inorganic fiber and a fiber mineral as needed. By adding the fiber, it is possible to increase the target rigidity of the molded body, and it is more difficult to crack, and it is difficult to crack by heat shock.

  For example, when a honeycomb is formed by extrusion, the fiber length is preferably shorter than the mouth of the die and the mesh. Therefore, sepiolite having a short fiber length or attapulgite is suitable for forming the honeycomb.

  In addition, examples of usable inorganic fibers include glass fibers, alumina fibers, carbon fibers, silicon carbide fibers, rock wool, titania whiskers, basic magnesium sulfate whiskers, stainless steel fibers, and other metal fibers. Examples of fiber minerals include wollastonite and asbestos, and various functions such as thermal conductivity, conductivity, photocatalytic properties, and flame retardancy can be selected by appropriately selecting fibers according to the purpose. Can be granted.

<Combination ratio>
This molded body is a molded body comprising adsorbent particles and a binder mainly composed of silicone, and the content of the adsorbent particles is 100 parts by mass with respect to the total amount of the adsorbent particles and the binder. 60 parts by mass or more and 90 parts by mass or less. That is, the content of the binder needs to be 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total amount of the adsorbent particles and the binder.
If the content of the adsorbent particles is 60 parts by mass or more with respect to 100 parts by mass of the total amount of the adsorbent particles and the binder, the amount of the adsorbent particles will not be too small, so that the adsorption performance can be maintained. it can. In addition, if the binder is 40 parts by mass or less, the adsorbent particles are not covered with the binder and the exposed surface of the adsorbent particles can be maintained. Can be prevented from decreasing. On the other hand, if the content of the adsorptive particles is 90 parts by mass or less, that is, if the binder is 10 parts by mass or more, the strength of the molded product can be maintained. One of the characteristics of this molded article is that the strength can be maintained with such a small amount of binder.

<Other materials>
(Plasticizer)
When producing a honeycomb by extrusion molding or the like, water is usually used as a solvent, and at that time, a plasticizer may be added for the purpose of imparting fluidity, shape retention and the like.
Examples of the plasticizer include water-soluble polymers, and examples thereof include cellulose ethers such as methyl cellulose, polysaccharides, and polyvinyl alcohol. In addition, these can be used individually or in mixture.

(Pore forming material)
In this molded object, it can be made porous by adding a pore former.
As the pore former used in the molded article, it is preferable to use fine particles that are thermally decomposed under firing conditions in which the binder can maintain rubber elasticity. By firing such a pore former after the binder (for example, silicone rubber) is cured, a porous zeolite compact without cracks can be obtained.
It is also possible to form pores by extracting the pore former with a solvent, in which case fine particles having high solubility in the solvent are preferred.

  Depending on the particle diameter of the pore former, the pore diameter of the molded body can be adjusted to some extent. In order to increase the adsorption rate, it is preferable to increase the surface area of the molded body. For this purpose, the particle diameter of the pore former is preferably as small as possible. From such a viewpoint, the average particle diameter of the pore former is preferably 0.1 μm to 100 μm, more preferably 0.5 μm to 50 μm. Moreover, you may use together what has several types and several particle diameter distribution for a pore former.

  The added amount of the pore former is preferably 10 vol% or more and 90 vol% or less with respect to the aggregate. If it is 10 vol% or more, the adsorption rate is improved, and if it is 90 vol% or less, it is preferable because the strength of the molded product can be maintained. From this point of view, it is more preferable that it is present at a ratio of 20 vol% or more, and it is more preferable that it is present at a ratio of 25 vol% or more. On the other hand, it is more preferable that it exists in the ratio of 70 vol% or less, and it is more preferable that it exists in the ratio of 60 vol% or less.

  The type of pore former is not particularly limited, and examples thereof include polymer particles such as crosslinked acrylic, polystyrene, polyacrylonitrile, sweet potato starch, corn starch and the like. The polymer particles can be used in a hollow shape or a core-shell type. In addition, for the purpose of enhancing dispersibility, the surface may be inorganically treated with calcium carbonate or the like.

<Physical properties and shape of the molded body>
The molded body preferably has the following physical properties.

(Microscopic structure)
As shown in FIG. 1, the molded body is partially bonded by a binder between the adsorbent particles and the adsorbent particles, the binder exhibits a discontinuous bonded phase, and the adsorbent particles are covered with the binder. It is preferred that the surface of the adsorbent particles is exposed. However, even if such a discontinuous bonded phase is exhibited, the discontinuous bonded phase has elasticity, and one of the features of the molded body is that the strength can be maintained.

  The structure as shown in FIG. 1 can be formed by drying water, burning pores, or other additives, and the surface of the adsorbent particles is more easily exposed when the binder is not hydrophilic.

(Storage elastic modulus of the molded product)
By using a silicone rubber having a small storage elastic modulus as the binder, the storage elastic modulus of the molded article can be set low even when the adsorbent particles are highly filled.
Regarding the storage elastic modulus of the molded body, although there is a width depending on the content rate and type of the adsorbent particles, the dynamic viscoelasticity was measured at a vibration frequency of 10 Hz from the viewpoint of ensuring the rigidity capable of self-supporting the molded body. It is preferable that the storage elastic modulus at normal temperature is 1.0 × 10 ⁸ Pa or more. On the other hand, from the viewpoint of relieving physical stress, it is preferably 5.0 × 10 ⁹ Pa or less.
In addition, the normal temperature in this invention is the temperature of the range of 5-35 degreeC.

(Hole diameter)
The pore diameter of the molded body is preferably 0.1 μm or more and 100 μm or less, although it depends on the shape and porosity of the molded body, the viscosity of the fluid to be adsorbed, and the like. If it is 0.1 micrometer or more, a fluid can fully be spread | circulated in the inside of a molded object. On the other hand, if the pore diameter is 100 μm or less, not only is the adsorption rate advantageous, but the strength of the molded body can be maintained.
Note that the pore diameter of the molded body can be controlled by the amount of pore former, the particle diameter, and the like.

(Porosity)
As for the porosity of the molded article, it is preferable that pores of 0.1 μm or more and 100 μm or less exist in a ratio of 10 vol% or more and 90 vol% or less.
If the porosity is 10 vol% or more, the adsorption rate is improved, and if it is 90 vol% or less, the strength of the molded product can be maintained. From this point of view, it is more preferable that pores of 0.1 μm or more and 100 μm or less exist in the molded body at a ratio of 20 vol% or more, and more preferable that they exist at a ratio of 25 vol% or more. On the other hand, it is more preferable that it exists in the ratio of 70 vol% or less, and it is more preferable that it exists in the ratio of 60 vol% or less.
In addition, the porosity of this molded object can be controlled by the particle diameter of the pore former, the addition amount, and the like.

(shape)
The molded body can be produced in an arbitrary shape such as a tubular shape, a cylindrical shape, a bead shape, a tablet shape, a pellet shape, a sheet shape, a strand shape, or a honeycomb shape. Above all, the surface shape can be increased and the adsorption performance can be improved if the honeycomb is formed by combining cells with a cross-sectional shape such as a circle, triangle, quadrangle, hexagon, etc. The body is preferably in the form of a honeycomb.

For example, it may be formed into a honeycomb shape or a cell shape, a tubular shape, a sheet shape, or a strand shape that can constitute the honeycomb, and a plurality of these may be combined to form a honeycomb shape.
At this time, according to the present molded body, the thickness of the cell wall of the honeycomb can be reduced, for example, 30 μm to 1000 μm, particularly 40 μm to 500 μm, and especially 50 μm to 300 μm. Can do.
If the cell wall thickness is reduced, the absolute amount of adsorptive particles decreases, and there is a risk of a decrease in the adsorption amount. However, by reducing the cell pitch, the cell density is increased and both the adsorption speed and the adsorption amount are achieved. Can be planned. As long as the strength of the molded body allows, it is desirable that the cell density is high, but the cell density is preferably 200 to 1200 cells / square inch.

<Manufacturing method>
Next, the manufacturing method of this molded object is demonstrated. A manufacturing method mainly by extrusion molding will be specifically described. However, it is not limited to the manufacturing method described below, and can be carried out in the same manner as the conventionally known general-purpose ceramic molding.

When manufacturing this molded object by extrusion molding, first, an absorptive particle, a binder, and raw materials, such as inorganic fiber, are mixed as needed and an aggregate is prepared.
Next, a pore former, a solvent, and a plasticizer as necessary are added to the aggregate and kneaded, and a plasticized dough is formed with an extruder.

More specifically, for example, an inorganic fiber is added to a synthetic zeolite powder, a room temperature curable silicone rubber, and a pore former, if necessary, mixed with a high speed mixer, and a plasticizer and a solvent are added thereto. Grain. Then, the obtained mixture may be kneaded with an extruder, a pressure kneader, a roll or the like to form a dough, and then charged into the extruder to be molded.
If the heat generated by the addition of the solvent is large, the solvent may be adsorbed in advance before adding the binder.

At this time, it is preferable to use water as the solvent.
Further, as the plasticizer, it is preferable to use a water-soluble polymer, and examples thereof include cellulose ethers such as methyl cellulose, polysaccharides, polyvinyl alcohol, and the like, and these may be used alone or in an arbitrary mixture. it can.
In addition, generally known lubricants, dispersants and the like can be added as necessary.

  It is preferable to find out conditions that give good plasticity and moldability to the raw material powder by adjusting the kind and amount of the plasticizer and the amount of water. For this reason, the formulation of water and the plasticizer differs depending on the raw material powder, but in general, the plasticizer is preferably 20% by mass or less based on the raw material powder. Further, when the moisture content is large, shrinkage during drying increases, and accordingly, the molded body is more likely to warp or crack.

  The method of extrusion molding is not particularly limited, and examples thereof include a method of extrusion molding using a die having a slit having a shape complementary to the cross-sectional shape of the molded body. In such a method, even when a molded body having a complicated shape such as a honeycomb shape or a monolith shape is formed, a honeycomb shape or a monolith having a desired cell shape, partition wall thickness, and cell density can be obtained by appropriately changing the shape of the slit. A shaped molded body can be easily obtained. There is no restriction | limiting in particular also about an extrusion molding machine, A conventionally well-known extrusion molding machine (For example, a vacuum kneader, a ram type extrusion molding machine, a biaxial continuous molding machine etc.) can be used conveniently.

  The molded body thus obtained may be dried. There is no particular limitation on the drying method, and conventionally known drying methods such as hot air drying, microwave drying, dielectric drying, reduced pressure drying, vacuum drying, freeze drying and the like can be used. However, in order to dry the entire molded body uniformly and without defects, it is preferable to gradually dry. Examples of the drying method capable of such an operation include low-temperature drying and humidity conditioning drying. In the case where the molded body has a cylindrical shape or the like, it is preferable to dry the molded body while rolling it using a roller, pressurized air, or the like. By carrying out like this, it can prevent that the dead weight of a molded object acts in one direction, and can suppress the deformation | transformation by the dead weight of a molded object effectively.

  When room temperature curable silicone rubber is used as the binder, the silicone rubber is crosslinked to some extent after drying, but by aging under high humidity, crosslinking proceeds and strength can be improved. Such a molded body can be easily cut with a blade or the like, and can suppress the occurrence of defects during processing. If the binder is a silicone rubber that needs to be heated for curing, it is crosslinked by heat treatment.

When the pore former is a thermally decomposable particle, it can be baked to make it porous.
The firing conditions are not particularly limited as long as the pore-forming material is decomposed. However, even if silicone rubber is formulated with a heat-resistant agent, if it exceeds 350 ° C., the physical properties are drastically lowered. The molded body is preferably fired at a temperature of 350 ° C. or lower, and more preferably at 300 ° C. or lower.
Also regarding the firing method, conventionally known firing equipment can be used.

  As a method for manufacturing the honeycomb, in addition to forming the honeycomb die by attaching the die to the extruder as described above, the honeycomb is manufactured by forming a sheet and corrugating and bonding the sheet. You can also.

<Application>
By making this molded body into a honeycomb shape, it can be made into a rotor-type adsorption element (digican rotor) and various filters, and these can be used to manufacture air conditioning devices such as humidity control devices and deodorization devices. it can.
In addition, it can be expected to be used for the same purpose by forming into a pellet by granulation and fixing it to a substrate.
Further, when the adsorptive particles also have a catalytic function, they can be used as fixed catalysts. Furthermore, the molded body can be formed into an appropriate shape, and can be suitably used for, for example, a gas separation and purification apparatus and a heat exchanger.

<Explanation of terms>
In the present invention, when expressed as “X to Y” (X and Y are arbitrary numbers), “X is preferably greater than X” and “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It is meant to include “less than”.
Further, in the present invention, when expressed as “more than X” (X is an arbitrary number), unless otherwise specified, it means “preferably greater than X” and includes “Y or less” (Y is an arbitrary number) When expressed as (numerical), it means “preferably smaller than Y” unless otherwise specified.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part.

<Evaluation method>
First, a method for preparing samples used in Examples and Comparative Examples and an evaluation method thereof will be described.

(Baking conditions)
Samples were baked in each evaluation of Examples and Comparative Examples. The firing conditions at this time will be described.

The firing conditions of Example 1 and Comparative Example 1 were set in a constant temperature and humidity chamber at 50 ° C. and 60% RH for 7 days, and subsequently baked at 300 ° C. with a baking test apparatus (Daeei Kagaku Seisakusho, DKS-5S). Baked at 100C for 100 minutes.
The firing conditions of Comparative Example 2 and Comparative Example 3 were fired at 600 ° C. for 2 hours in a muffle furnace (Yamato Kagaku, FM-27).
The baking conditions of Comparative Example 4 and Comparative Example 5 were baked at 250 ° C. for 100 minutes with a baking test apparatus (Daeei Kagaku Seisakusho, DKS-5S).

(Preparation of cured binder and evaluation of rubber elasticity)
The binders used in the examples and comparative examples were fired under the respective firing conditions to prepare a sheet-like binder cured product having a thickness of 0.5 mm. The obtained sheet-like cured binder was compressed in the thickness direction using a caliper in a room temperature room, and when the thickness reached 80%, the load was released and the thickness of the same part was measured after 1 minute. At this time, if the thickness is restored to 99% or more before compression, it can be recognized as the rubber elastic body of the present invention at room temperature.

(Storage elastic modulus of the cured binder)
The storage elastic modulus at each temperature of the cured binder used in Examples and Comparative Examples was measured at a vibration frequency of 10 Hz using a dynamic viscoelasticity measuring device DVA-200 (manufactured by IT Measurement Control Co., Ltd.). .

(Preparation of paste)
As shown in Table 1, synthetic resin that can be regenerated at low temperature as adsorptive particles, manufactured by Mitsubishi Plastics, Inc., trade name: AQSOA FAM-Z05 (zeolite structure AFI, aluminophosphate, pore size 7.3 mm, 75 parts of average particle diameter D50: 5 μm), fiber mineral, made by TOLSA, trade name: 10 parts of PANGEL AD (Sepiolite), 15 parts of binder as solid content were mixed to prepare an aggregate composition.

In the case of performing porosity in Examples and Comparative Examples, the total amount of aggregate was adjusted to 30 g, and ion-exchanged water as a solvent was 62 parts (18.6 g) with respect to 100 parts by mass of aggregate. Product name: Shin-Etsu Chemical Co., Ltd., trade name: METROOSE 90SH30000, 7.3 parts (2.2 g) with respect to 100 parts by mass of aggregate, and pore-forming material, GANTZ Kasei Co., Ltd., trade name: Gantzpearl GM-1001 (polymethylmethacrylate particles, average particle diameter D50 is 10 μm) is added to 50 parts by mass of the aggregate blend, and the conditions are 30 rpm and 20 to 30 ° C. in a laboratory plast mill manufactured by Toyo Seiki. And kneaded for 15 minutes to obtain a dough.
On the other hand, in the case where the porosity is not used in the examples and comparative examples, the total aggregate blend is prepared to be 40 g, and 46.5 parts of ion-exchanged water as a solvent with respect to 100 parts by mass of the aggregate blend ( 18.6 g), made by Shin-Etsu Chemical Co., Ltd. as a plasticizer, 5.5 parts (2.2 g) is added to 100 parts by mass of the aggregates Metroze 90SH30000, and added to Toyo Seiki's Laboplast Mill And kneading for 15 minutes under conditions of 30 rpm and 20 to 30 ° C. to obtain a dough.
In addition, the numerical value in a frame of Table 1 shows a mass part, and the numerical value in () has shown the value converted into solid content. Moreover, the mass part of a pore former, water, and a plasticizer is a mass part when aggregate composition is 100 mass parts.

(Preparation of fired sheet and evaluation of water absorption and adsorption rate)
The kneaded clay obtained in Examples and Comparative Examples was pressed at room temperature, dried, and fired under the respective firing conditions to obtain fired sheets having a thickness of 0.9 mm. The obtained fired sheet was cut into a size of 50 × 50 mm, and the weight change in a room at 25 ° C. and 48% RH was recorded with an electronic balance. The difference between the weight reached in the room and reached the saturated state and the weight in the dry state was defined as the saturated water absorption, and the weight increase from the dry state divided by the saturated water absorption was defined as the water absorption. The water absorption after 10 minutes was determined as an index of the adsorption rate.
Water absorption after 10 minutes (%) = (Increased weight after 10 minutes from dry state) / (Saturated water absorption in the room) × 100
Here, when the water absorption rate after 10 minutes is 15% or more, the adsorption rate evaluation “◯”, 10% or more and less than 15% is the adsorption rate evaluation “Δ”, and less than 10% is the adsorption rate evaluation “ X ”and listed in Table 1.

(Preparation of fired strip-shaped compact and 3-point bending test)
Using a flow tester equipped with a slit nozzle (lip gap: 1 mm, width: 8 mm), the kneaded material obtained in the examples and comparative examples was molded into a 1 mm thick sheet at room temperature, and the resulting sheet was thick. The strips were processed into strips having a thickness of 1 mm, a width of 5 mm, and a length of 40 mm, and fired under the respective firing conditions to obtain a fired strip-shaped molded body.
A fired strip-shaped molded body having a thickness of 1 mm, a width of 5 mm, and a length of 40 mm produced in this manner was subjected to a displacement speed of 1 mm / min and a span of 16 mm with an electromagnetic force micro tester MMT-250N (manufactured by Shimadzu Corporation). A three-point bending test was performed at, and the results are shown in FIG.

  Here, in order to make a relative comparison, the strength of the comparative example 5 is “Δ”, and the area under the load-stroke curve in FIG. Those were defined as “x” and listed in Table 1.

<Example 1>
Condensation type silicone RTV rubber as binder, manufactured by Momentive Performance Materials Japan GK, trade name: TSE3826 (polyalkylsiloxane as base polymer, oxime silane as crosslinking agent, dialkyltin compound as catalyst, inorganic particles) (Including iron oxide and silica) was used to make the pores. The number of blending parts is as shown in Table 1.

As a result of evaluating the rubber elasticity of the cured binder, the binder used in Example 1 was restored to 100%. Therefore, it was confirmed that the binder used in Example 1 was a rubber elastic body defined in the present invention at room temperature even after firing.
Moreover, the storage elastic modulus of binder hardened | cured material is shown in FIG. The storage elastic modulus at 20 ° C. of the cured binder product of Example 1 was 1.26 × 10 ⁶ Pa. The storage elastic modulus at 0 ° C. was 1.28 × 10 ⁶ Pa, and the storage elastic modulus at 150 ° C. was 1.31 × 10 ⁶ Pa. Therefore, it was in the range of the storage elastic modulus at room temperature of 1 to 10 MPa, which is generally said to be exhibited by a rubber elastic body. Moreover, it turned out that the substantially constant storage elastic modulus is maintained in the temperature range of 0-250 degreeC.

  The water absorption after 10 minutes was 20.4%, and the evaluation of the adsorption rate was “◯”.

As a result of the three-point bending test of the fired strip-shaped body, the stroke at break was 0.55 mm, the load was 1 N, and the area under the load-stroke curve in FIG. Therefore, the strength was evaluated as “◯”.
From the above results, the molded body obtained in Example 1 has a discontinuous binder phase due to porosity, and the cured binder made of curable silicone has rubber elasticity. It can be considered that there is little change, and it is possible to improve both the strength of the molded body and the adsorption speed as compared with the prior art.

<Comparative Example 1>
The same binder as in Example 1 was used, and no porosification was performed. The number of blending parts is as shown in Table 1.

  The binder is the same as in Example 1, and the rubber elasticity evaluation and the storage elastic modulus of the cured binder are the same as in Example 1.

  The water absorption after 10 minutes was 8.7%, and the adsorption rate was evaluated as “x”.

As a result of the three-point bending test of the fired strip-shaped molded body, even if the stroke exceeds 0.7 mm, it is not broken, and the area under the load-stroke curve in FIG. The strength was evaluated as “◯”.
As described above, the strength of the molded body obtained in Comparative Example 1 was sufficient, but the adsorption rate was considerably low.

<Comparative example 2>
The product name: Snowtex N-40 made by Nissan Chemical Co., Ltd. was used as a binder as a binder, and only the same mass part as Example 1 was added. The solid content was 40% by mass. Porosification was performed. The number of blending parts is as shown in Table 1.

As a result of evaluation of rubber elasticity of the cured binder, it was brittle fractured before being compressed to 90%. That is, it was not a rubber elastic body defined in the present invention.
Further, the storage elastic modulus of the cured binder was not measurable because the cured silica sol was very brittle.

  The water absorption after 10 minutes was 20.6%, and the evaluation of the adsorption rate was “◯”.

In the three-point bending test of the fired strip-shaped body, a strip that can be bent was not obtained. Therefore, since it was so brittle that it could not be measured, the strength was evaluated as “×”.
As described above, the molded body obtained in Comparative Example 2 had a good adsorption rate, but the molded body was brittle and insufficient in strength.

<Comparative Example 3>
The same binder as in Comparative Example 2 was used, and no porosification was performed. The number of blending parts is as shown in Table 1.

  The binder was the same as in Comparative Example 2 and was not a rubber elastic body defined in the present invention, and the storage elastic modulus was not measurable as in Comparative Example 2.

  The water absorption after 10 minutes was 12.2%, and the evaluation of the adsorption rate was “Δ”.

As a result of the three-point bending test of the fired strip-shaped body, the stroke at break is 0.10 mm, the load at break is 1.5 N, and the area under the load-stroke curve in FIG. Since it was smaller than Comparative Example 5, the strength was evaluated as “x”.
As described above, the molded body obtained in Comparative Example 3 was insufficient in terms of the adsorption rate and the strength of the molded body, and was not compatible.

<Comparative Example 4>
Asahi Kasei Wacker Silicone Co., Ltd., trade name: SILRES MSE100 was used as a solid content as a binder, and only the same mass part as in Example 1 was added. Porosification was performed. The number of blending parts is as shown in Table 1.

  SILRES MSE100 is a methyl ester oligomer of various methylsilicic acid mixtures, and reacts by hydrolysis and condensation to give a hard silicon resin. Its molecular weight is about 480 g / mol to about 600 g / mol. The solid content after heat treatment at 250 ° C. for 2 hours was 55% by mass.

As a result of evaluation of rubber elasticity of the cured binder, it was brittle fractured before being compressed to 90%. That is, it was not a rubber elastic body defined in the present invention.
Further, the storage elastic modulus of the binder cured product was very fragile and could not be measured.

  The water absorption after 10 minutes was 17.8%, and the adsorption rate was evaluated as “◯”.

As a result of the three-point bending test of the fired strip-shaped body, the stroke at break was 0.23 mm, the load was 1.3 N, and the area under the load-stroke curve in FIG. Therefore, the strength was evaluated as “×”. It was found that the elasticity was higher than that of Example 1 and physical stress could not be absorbed or alleviated.
As described above, the molded body obtained in Comparative Example 4 had a slightly slower adsorption rate and insufficient strength of the molded body as compared with Example 1.

<Comparative Example 5>
The same binder as in Comparative Example 4 was used, and no porosity was implemented. The number of blending parts is as shown in Table 1.

  The binder was the same as in Comparative Example 4 and was not a rubber elastic body defined in the present invention, and the storage elastic modulus was not measurable as in Comparative Example 4.

  The water absorption after 10 minutes was 9.9%, and the evaluation of the adsorption rate was “x”.

As a result of the three-point bending test of the fired strip-shaped body, the stroke at the time of breakage is 0.2 mm, and the load is 2.4 N. In order to make a relative comparison of strength, Comparative Example 5 was evaluated as strength “Δ”. It was found that the elasticity was higher than that of Example 1 and physical stress could not be absorbed or alleviated.
As described above, the molded body obtained in Comparative Example 5 showed a slight improvement in strength compared to Comparative Example 3 using silica sol as a binder, but the adsorption rate was insufficient.

From Table 1, Example 1 prescribed | regulated by this invention was good in both adsorption rate and intensity | strength, and Comparative Examples 1-5 was inadequate in either adsorption rate or intensity | strength.
In Example 1, since the binder phase is rubber elastic in a wide temperature range, physical stress can be alleviated and the molded body is not easily broken. However, as shown in Comparative Example 1, a rubber elastic binder is used. If the pore formation was not performed, there was a problem that the adsorption ability of the adsorbent particles could not be sufficiently exhibited and the adsorption rate was low.
In Comparative Examples 2 to 5, since the binder phase is highly elastic and cannot relieve physical stress, it is made porous as in Comparative Example 2 or 4, and the continuity or uniformity of the binder phase is lost. It was found that it was easily destroyed by stress concentration.

  According to the present invention, it has been found that even if the adsorbent particles are as high as 60 parts by mass or more, it is possible to obtain a molded body having a strength and adsorption rate higher than those of the prior art. It was also found that the manufacturing cost can be reduced because the firing temperature is low while maintaining sufficient heat resistance. Furthermore, by adjusting the formulation of the pore former and binder, it is possible to produce molded articles with the desired strength and adsorption capacity, and the degree of freedom in design can be increased. Is available.

Claims (11)

  A molded article comprising adsorbent particles and a binder comprising a curable silicone composition, wherein the binder has rubber elasticity at room temperature, and the content of the adsorbent particles is an adsorbent particle. And the molded object characterized by being 60 mass parts or more and 90 mass parts or less with respect to 100 mass parts of total amounts of a binder, and being porous by the pore former.   A molded article, wherein the binder according to claim 1 is a condensation type curable silicone composition.   The molded article according to claim 1 or 2, wherein the adsorptive particles are one type or two or more types selected from the group consisting of zeolite, silica gel, mesoporous silica, and activated carbon.   The adsorptive particles are one type of zeolite selected from the group consisting of aluminosilicates and aluminophosphates, or a zeolite consisting of a combination of two or more types. The molded body described.   The formed body according to any one of claims 1 to 4, wherein the formed body has a honeycomb shape.   The desiccant rotor which uses the molded object in any one of Claims 1-5.   An air conditioner using the desiccant rotor according to claim 6.   The filter which uses the molded object in any one of Claims 1-5.   An air conditioner using the filter according to claim 8.   The fixed catalyst which uses the molded object in any one of Claims 1-5.   The method for producing a molded body according to any one of claims 1 to 5, wherein firing is performed at a temperature of 350 ° C or lower.

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