JP4691985B2 - Resin molded body, resin composition, paint using the same, and method for producing resin molded body - Google Patents

Description

  The present invention relates to a resin molded body containing a binder resin and silica, a resin composition and a coating material using the same, and a method for producing the resin molded body, and in particular, it can remarkably exhibit the absorption / release performance of silica. The present invention relates to a possible resin molded body, a resin composition, a paint using the same, and a method for producing the resin molded body.

  Conventionally, resin compositions have been used as materials constituting various things from buildings to electrical appliances. Here, the resin composition is a mixture of a binder resin and some material, and various functions can be exhibited not only by the type of the binder resin but also by the mixed material.

  Thus, silica is often used as a material to be mixed with the binder resin. Silica is a substance having various functions and is widely used as an effective material contained in a resin composition (Patent Document 1).

Japanese Patent No. 3398830

  Silica has various functions resulting from its fine pore structure. For example, various substances can be adsorbed in the pores. However, conventionally used resin compositions in which silica is mixed with a binder resin, the binder resin blocks or fills the pores of the silica. There was a problem that it was not fully demonstrated. Here, the absorption / release performance refers to various performances that are manifested by the property of adsorbing silica substances, such as the adsorption performance of silica to adsorb substances in the pores and the release performance of releasing adsorbed substances. That means.

  The present invention was devised in view of the above-described problems, and provides a resin molded body and a resin composition having improved absorption / release performance as compared with the prior art, a paint using the resin composition, and a resin molding thereof. It aims at proposing the manufacturing method of a body.

That is, the gist of the present invention is a resin molded body comprising at least a binder resin and silica, and 63 % or more of the pore volume of the silica is open to the outside of the resin molded body, The resin molded body satisfies the following conditions (a) to (f) (claim 1).

(A ) The pore volume of the silica is 0.3 ml / g or more and 3.0 ml / g or less.
(B) The specific surface area of the silica is 100 m ² / g or more and 1000 m ² / g or less.
(C) The mode pore diameter of the silica is 2 nm or more and 50 nm or less.
(D) the average particle diameter of the silica exceeds 2 μm, and the total volume of pores in the range of ± 20% of the value of the most frequent pore diameter (D _max ) is 50% or more of the total volume of all the pores .
In the solid Si-NMR measurement of (e) the silica, -OSi are three bonded Si ^{(Q 3)} and -OSi of ^Q 4 / ^{Q 3} in which a molar ratio of four bonded Si ^{(Q 4)} The value is 1.4 or more.
(F) The silica is obtained by hydrolyzing silicon alkoxide and hydrothermally treating it.

Further, the resin molded body, as well as further comprising a substrate, at least a portion of the substrate, it is preferable that the silica is fixed by the binder resin (claim 2).
Furthermore, it is preferable that the base material is composed of at least a fiber (claim 3 ) .

Moreover, it is preferable that the glass transition temperature of binder resin is -80 degreeC or more and 110 degrees C or less (Claim 4 ).
Further, the resin molded body is obtained by mixing the binder resin, the silica, and a solvent and removing the solvent, and the binder resin becomes a colloid in the solvent to form an emulsion. It is preferable that it is a thing (Claim 5).

  ADVANTAGE OF THE INVENTION According to this invention, the resin molded object excellent in the absorption / release performance, the resin composition, the coating material using the same, and the manufacturing method of a resin molded object can be provided. In addition, these resin moldings exhibit at least one of hygroscopicity, moisture releasing properties, moisture conditioning properties, adsorption exothermic properties (especially hygroscopic exothermic properties), sustained release properties of supported drugs, and deodorizing properties. Can do.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention. .
[I] Resin molding of the present invention:
The resin molded body of the present invention (hereinafter abbreviated as “the molded body of the present invention” as appropriate) is a resin molded body composed of at least a binder resin and silica, and 30% or more of the pore volume of silica It is characterized by being open to the outside of the molded article of the invention.

  Here, that the pore volume of the silica is open to the outside of the molded body of the present invention means that the inside of the silica pores communicates with the outside of the molded body of the present invention. By opening the pores to the outside of the molded body, the molded body of the present invention can absorb moisture, release moisture, adjust humidity, exothermic adsorption (especially hygroscopic exothermic), sustained drug release, adsorptive, deodorant. It is possible to exhibit various absorption and release performances that are manifested with the property that silica adsorbs substances, such as properties and antibacterial properties, more effectively than before.

[1] Silica:
There is no limitation on the silica contained in the molded article of the present invention, and any silica can be used. From the viewpoint of reliably opening the pores to the outside of the molded article, the following silica (hereinafter referred to as “the present invention” It is preferable to use “silica”. Moreover, in this invention, a silica may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
In the present invention, “silica” refers to hydrous silicic acid. Furthermore, not only pure silica formed only with hydrous silicic acid but also silica containing other components such as metals and organic substances and / or supported thereon are treated as silica. The hydrous silicic acid is represented by the SiO ₂ .nH ₂ O characteristic formula (where n is a positive number). In the present invention, the effect is remarkable in so-called “silica gel” or micelle template type silica among silica. Silica is widely known to be a porous body having many pores.

[1-1] Configuration of silica of the present invention:
The silica of the present invention satisfies at least the following conditions (a) to (c).
(A) The pore volume of silica is 0.3 ml / g or more and 3.0 ml / g or less.
(B) The specific surface area of silica is 100 m ² / g or more and 1000 m ² / g or less.
(C) The mode pore diameter of silica is 2 nm or more and 50 nm or less.

・ Condition (a)
The silica of the present invention has a pore volume value measured by a nitrogen gas absorption / desorption method of usually 0.3 ml / g or more, preferably 0.4 ml / g or more, more preferably 0.6 ml / g or more, More preferably 0.8 ml / g or more, and usually 3.0 ml / g or less, preferably 2.5 ml / g or less, more preferably 2.0 ml / g or less, still more preferably 1.6 ml / g. It is as follows. Thereby, the molded object of this invention can exhibit high absorption-and-release performance. The pore volume can be determined from the amount of nitrogen gas adsorbed at an adsorption isotherm relative pressure of 0.98.

・ Condition (b)
The silica of the present invention has a specific surface area of pores of usually 100 m ² / g or more, preferably 200 m ² / g or more, more preferably 300 m ² / g or more, and further preferably 350 m ² / g or more. Particularly preferably, it is 400 m ² / g or more, usually 1000 m ² / g or less, preferably 900 m ² / g or less, more preferably 800 m ² / g or less, and further preferably 700 m ² / g or less. The value of the specific surface area is measured by the BET method by nitrogen gas adsorption / desorption.
As described above, since the silica of the present invention has a large specific surface area, the interaction area between the adsorbing substance adsorbed in the pores and silica can be increased in the molded body of the present invention. Therefore, the interaction with the substance can be largely adjusted by changing the surface state of the silica pores.

・ Condition (c)
Further, the silica of the present invention is described in EP Barrett, LG Joyner, PH Haklenda, J. Amer. Chem. Soc., Vol. 73, 373 (1951) from an isothermal desorption curve measured by a nitrogen gas adsorption / desorption method. A pore distribution curve calculated by the BJH method, that is, a graph in which a differential nitrogen gas adsorption amount (ΔV / Δ (logd); V is a nitrogen gas adsorption volume) is plotted against the pore diameter d (nm). The most frequent pore diameter (D _max ) is usually 2 nm or more, and usually 50 nm or less, preferably 30 nm or less, more preferably 20 nm or less, still more preferably 17 nm or less, and particularly preferably 15 nm or less. If the mode pore diameter (D _max ) is smaller than the above range, the space in the silica becomes small, so that the absorption / release performance may be deteriorated. If it is larger than the above range, the strength of the silica is weak. As a result, the pore structure of silica breaks with time or the binder resin easily enters the pores, so that the absorption / release performance may be lowered. In addition, as for the silica of this invention, it is desirable to be able to use properly what has various mode pore diameters ( _Dmax ) according to a use.

  Further, the silica of the present invention is hydrothermally treated during production as described later, and the pore diameter can be arbitrarily adjusted by adjusting the temperature condition of the hydrothermal treatment. Among the absorption / release performances exhibited by the molded article of the present invention, there are those that exhibit the performance according to the pore diameter, and therefore it is desirable to appropriately set the pore diameter according to the application. For example, in humidity control among the absorption / release performance, the humidity adjusted by silica generally depends on the pore diameter.

  The silica of the present invention is not limited as long as the above conditions (a) to (c) are satisfied, but usually the following conditions are satisfied in addition to the above conditions (a) to (c). It is desirable.

・ Condition (d)
The silica of the present invention has a total pore volume in the range of ± 20% of the value of the most frequent pore diameter (D _max ). For example, for silica having an average particle diameter of 2 μm or less, the total pore volume It is usually 20% or more, preferably 30% or more, more preferably 40% or more. For example, in silica having an average particle diameter exceeding 2 μm, the total volume of pores in the range of ± 20% of the value of the most frequent pore diameter (D _max ) is usually 50% of the total volume of all pores. Above, preferably 60% or more, more preferably 70% or more. This means that the diameters of the pores of the silica of the present invention are uniform in the pores near the most frequent pore diameter (D _max ), that is, the distribution of pore diameters (pore diameters) is extremely narrow (sharp). Means). The upper limit of this ratio value is not particularly limited, but is usually 90% or less. When a partially brittle portion is generated in silica, the pore structure of the portion is easily broken. However, if the pore size distribution is small as described above, the structure of the silica of the present invention will be uniform, and therefore it will be difficult for the silica strength to vary and prevent the formation of partially fragile parts. Can do. For this reason, the whole molded object of this invention can exhibit high durability stably. Furthermore, it becomes possible to accurately control that the binder resin having a specific resin size enters the pores. In addition, when the pore size distribution of the silica is sharp, the functions of the moisture control property, moisture absorption exothermic property, sustained release property and the like are enhanced. Therefore, the molded product of the present invention including this has high humidity control property, moisture absorption exothermic property, sustained release property. It becomes possible to demonstrate.

・ Condition (e)
In relation to such characteristics, the silica of the present invention has a differential pore volume ΔV / Δ (logd) at the mode pore diameter (D _max ) calculated by the BJH method of usually 2 ml / g or more, Preferably it is 3 ml / g or more, more preferably 5 ml / g or more, usually 40 ml / g or less, preferably 30 ml / g or less, more preferably 25 ml / g or less, still more preferably 20 ml / g or less, Particularly preferably, it is desirable to be 12 ml / g or less {in the above formula, d is a pore diameter (nm) and V is a nitrogen gas adsorption volume}. When the differential pore volume ΔV / Δ (logd) is included in the above range, it can be said that the absolute amount of pores aligned in the vicinity of the most frequent pore diameter (D _max ) is extremely large.

・ Condition (f)
Further, in addition to the characteristics of the pore structure described above, the silica of the present invention is preferably amorphous, that is, a crystalline structure is not recognized in view of the three-dimensional structure. This means that when the silica of the present invention is analyzed by X-ray diffraction, a crystalline peak is not substantially observed. In this specification, non-amorphous silica means at least one crystal structure peak (crystallinity peak) at a position exceeding 0.6 nanometer (nm Units d-spacing) in the X-ray diffraction pattern. Refers to what is shown. Examples of such silica include micelle template silica that forms pores using an organic template. Amorphous silica is extremely excellent in productivity as compared with crystalline silica.

・ Condition (g)
Furthermore, regarding the structure of the silica of the present invention, a characteristic result can be obtained even by analysis by solid-state Si-NMR measurement.
Silica is a hydrate of amorphous silicic acid and is represented by the SiO ₂ .nH ₂ O characteristic formula, but structurally, O is bonded to each vertex of the Si tetrahedron, It has a structure in which Si is further bonded to O and spreads in a net shape. In some repeating units of Si—O—Si—O—, some of O is substituted with other members (for example, —H, —CH _3, etc.). As shown in the following formula (A), there are Si (Q ⁴ ) having ⁴ —OSi, Si (Q ³ ) having 3 —OSi as shown in the following formula (B), etc. In the formulas (A) and (B), the tetrahedral structure is ignored and the Si—O net structure is represented in a plane. In the solid Si-NMR measurement, the peaks based on the respective Si are called Q ⁴ peak, Q ³ peak,.

In the silica of the present invention, Q ⁴ / Q ³ indicating the molar ratio of Si (Q ³ ) bonded with three —OSi and Si (Q ⁴ ) bonded with four —OSi in solid-state Si-NMR measurement. Is usually 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more, and still more preferably 1.5 or more. The upper limit is not particularly limited, but is usually 10 or less.

In general, it is known that the higher this value, the higher the thermal stability of the silica. From this, it can be seen that the silica of the present invention is extremely excellent in thermal stability. That is, since the silica of the present invention is less likely to break the structure due to heat, the molded body of the present invention can be used stably over a long period of time. On the other hand, some crystalline micelle template silicas have a Q ⁴ / Q ³ value of less than 1.2 and have low thermal stability, particularly hydrothermal stability.

Incidentally, Q ⁴ / Q ³ and the value of the chemical shift of Q ⁴ peak, which will be described later, performs a solid Si-NMR measurement can be calculated based on the result. Further, analysis of measurement data (determination of peak position) is performed by a method of dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function.

・ Condition (h)
In addition, the silica of the present invention has one of its features that even when subjected to a heat treatment (hydrothermal resistance test) in water, the change in pore characteristics is small. Changes in the pore characteristics of silica after the hydrothermal resistance test are observed as changes in physical properties related to porosity such as specific surface area, pore volume, and pore size distribution. For example, in the silica of the present invention, when subjected to a hydrothermal resistance test at 200 ° C. for 6 hours, the specific surface area after the test is 20% or more with respect to the specific surface area before the test (the specific surface area residual ratio is 20% or more). ) Is preferable. The silica of the present invention having such characteristics is preferable because the porous characteristics are not lost even under severe use conditions for a long time. The residual ratio of the specific surface area is preferably 35% or more, particularly 50% or more.

  The silica of the present invention has very little deterioration of the characteristic that the pore diameter distribution is sharp and the change in the pore volume is very small or the pore volume is increased even after the hydrothermal treatment test. It has a characteristic that is not found in conventional silica.

  The hydrothermal resistance test in the present invention is to bring water at a specific temperature (200 ° C.) into contact with silica for a certain time (6 hours) in a closed system, and all the silica is in water. If present, the closed system may be completely filled with water, or a part of the system may have a gas phase part under pressure, and the gas phase part may contain water vapor. In this case, the pressure in the gas phase part may be, for example, 60000 hPa or more, preferably 63000 hPa or more. The error of the specific temperature is usually within ± 5 ° C., preferably within ± 3 ° C., particularly preferably within ± 1 ° C.

・ Condition (i)
Further, the silica of the present invention has a particle size of usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, and usually 300 μm or less, preferably 250 μm or less, more preferably 200 μm or less. When the particle diameter is within this range, it is easy to uniformly disperse the silica when the silica of the present invention is used in paints and molded articles. In particular, when fibers are used as the base material, the silica particle size is usually 0.1 μm or more, particularly 0.2 μm or more, from the viewpoint of the texture of the material (base material + resin molded body) and washing durability. Usually, it is preferably 5 μm or less, more preferably 2 μm or less.

・ Condition (j)
In addition, it is desirable that the silica of the present invention has less distortion in the bond angle of the siloxane bond forming the skeleton. Here, the structural strain of silica can be expressed by the value of the chemical shift of the Q ⁴ peak in the solid-state Si-NMR measurement.
Above, and the structural distortion of silica, in terms of association with the values of said Q ⁴ peak chemical shift, silica of the present invention, when the chemical shift of the above Q ⁴ peak δ and (ppm) Δ is the following formula (1)
−0.0705 × (D _max ) −11.36> δ (1)
(That is, the value of δ is smaller than the value {−0.0705 × (D _max ) −11.36} represented by the left side of the above formula (1) (exists on the minus side)). desirable. In the present specification, “ppm” represents a ratio to weight.

In the conventional silica, the chemical shift value δ of the Q ⁴ peak is generally larger (existing on the plus side) than the value calculated based on the left side of the above formula (I). Therefore, the silica of the present invention has a smaller value of the chemical shift of the Q ⁴ peak as compared with the conventional silica. This is nothing but the fact that the chemical shift of the Q ⁴ peak exists in a higher magnetic field in the silica of the present invention, and as a result, the bond angle represented by two —OSi with respect to Si is more uniform. Yes, meaning less structural distortion.

In the silica of the present invention, the chemical shift δ of the Q ⁴ peak is preferably less than the value calculated based on the left side (−0.0705 × (D _max ) −11.36) of the above formula (1). The value is smaller than 05%, more preferably smaller than 0.1%, and particularly preferably smaller than 0.15%. Usually, the minimum value of the Q ⁴ peak of silica gel is −113 ppm.

The silica of the present invention has excellent heat resistance, water resistance and the like, and hardly changes in physical properties. Therefore, the humidity control function is maintained for a long time even under high temperature and high humidity. The relationship between such a point and the structural strain as described above is not necessarily clear, but is estimated as follows. In other words, silica is composed of aggregates of spherical particles of different sizes, but in the state where there is little structural distortion as described above, a high degree of microstructural homogeneity of the entire spherical particles is maintained. Therefore, as a result, it is considered that excellent heat resistance, water resistance and the like are expressed. In addition, since the peak of Q ³ or less is limited in the spread of the net structure of Si—O, structural distortion of silica hardly appears.

Further, the silica of the present invention generally has a total content of metal elements (metal impurities) excluding silicon constituting the skeleton of the silica in order to improve durability, heat resistance, water resistance, etc. Is 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less. Thus, if there is little influence of an impurity, excellent properties, such as durability, heat resistance, and water resistance, can be expressed. In addition, since there are few metal impurities, in the molded body of the present invention containing the silica of the present invention, it is possible to suppress light deterioration, thermal deterioration, deterioration with time, etc. due to contact between the binder resin and the metal impurities. The molded body of the present invention can be used stably over a long period of time.
However, as will be described later, the silica of the present invention can acquire an advantageous function by intentionally containing other components such as a specific atom or atomic group depending on its use and the like. There is also. Therefore, whether or not to contain a component other than silica in the silica of the present invention should be selected according to its use.

  Moreover, the silica of this invention may have the other component of a silica as mentioned above. There are no particular restrictions on the other components that the silica of the present invention may have, and various auxiliary agents, simple elements and / or compounds of useful elements (hereinafter referred to as “useful different elements” as appropriate), organic groups (hereinafter referred to as “substances”) Optionally, it may contain and / or carry any component such as “useful organic group”).

  In addition, if the said other component can be contained in the molded object of this invention (and the resin composition of this invention mentioned later and the coating material of this invention) in the state which does not lose the target function, which In such a state, it may be contained in any step of the manufacturing process. For example, in addition to containing and / or supporting in silica, it may be used by being appropriately contained in a binder resin, or may be contained in a solvent used for paint or the like. Moreover, the coating material mentioned later may be used in the coating material during preparation or after preparation, and may be used in the resin molding body during or after preparation of the resin molding. In addition, when containing and / or supporting silica as described above, there is no limitation on the method of inclusion / supporting on silica, but for example, a method of containing and supporting an auxiliary agent during or after the production of silica. In addition, there is a method of supporting the silica in the molded body after manufacturing the resin molded body. In addition, the additives described later may also be supported on silica in advance. Furthermore, these auxiliaries and additives may be finally added by an operation such as impregnation after the raw material (resin molded body + base material) is produced. Furthermore, one type of auxiliary agent may be used alone, or two or more types may be used in any combination and ratio.

If the specific example of another component is given, you may carry | support the exothermic adjuvant as an auxiliary | assistant in the silica of this invention for the purpose of improving the hygroscopic exothermic property further. In addition, exothermic auxiliary agent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
As the exothermic auxiliary agent, any substance having a hygroscopic exothermic property can be used. For example, JP-B-7-59762, JP-A-9-158040, JP-A-2002-212880, JP-A-2000. A polymer compound having a hygroscopic exothermic property (hereinafter referred to as “hygroscopic exothermic polymer” as appropriate) described in JP-A-129574 and the like can be used. Explaining each of the patent publications exemplified here, Japanese Patent Publication No. 7-59762 describes a fiber product having hygroscopic heat generation. Japanese Patent Application Laid-Open No. 9-158040 discloses a material having a moisture absorption exothermic property and the like obtained by modifying an acrylic fiber to have a high moisture absorption property. Japanese Patent Laid-Open No. 2002-212880 discloses a technique for coating a fiber surface with a hygroscopic exothermic polymer. Furthermore, Japanese Patent Application Laid-Open No. 2000-129574 describes a technique for adhering fine particles of a hygroscopic exothermic polymer to the fiber surface.

  When exothermic auxiliary agents such as hygroscopic exothermic polymers are supported on the silica of the present invention, since the silica of the present invention has a large specific surface area, it is supported on the surface compared to conventional hygroscopic exothermic products. The specific surface area of the generated exothermic auxiliary agent is remarkably increased, and it is possible to exhibit a higher hygroscopic exothermic property than before.

  Specific examples of the hygroscopic exothermic polymer include vinyl carboxylic acids such as acrylic acid, methacrylic acid and maleic acid; 2-acrylamido-2-methylpropanesulfonic acid (AMPS), sodium 2-acrylamido-2-methylpropanesulfonic acid (AMPS). -Na), 2-aryloxy-2-hydroxypropane sulfonic acid, polymer compounds in which water-absorbing monomers such as vinyl sulfonic acid such as sodium styrene sulfonate are polymerized, and polysaccharides such as starch and cellulose. Of these water-absorbing monomers, acrylic acid, methacrylic acid, AMPS, and sodium styrenesulfonate are preferable. The hygroscopic exothermic polymer may be a polymer using one kind, or a copolymer or graft polymer using two or more kinds in combination in any combination and ratio. Furthermore, a polymer or copolymer using a monomer other than those exemplified in combination with a water-absorbing monomer may be used as the hygroscopic exothermic polymer. In that case, it is preferable that the ratio of the water-absorbing monomer is large.

Furthermore, in relation to the application to which the present invention is applied, when the technique of the present invention is used for daily goods such as disposable diapers, bedding, and clothing, the hygroscopic exothermic polymer may be a polyacrylic acid-based polysulfonate. Preferred examples thereof include synthetic polymer polymers such as poly (vinyl alcohol) / polyacrylate copolymer systems, starch polymers such as graft polymerization systems and carboxymethylation systems, and cellulose polymers. Table 1 shows examples of main types and structures of the hygroscopic exothermic polymers exemplified here. However, in the following Table 1, m ₁ , m ₂ and m ₃ each independently represent a number of 0 or more.

  In addition, when the technique of the present invention is used for fibers, the hygroscopic exothermic polymer is preferably polyacrylic acid, polyacrylic acid salt, polyacrylamide, polyvinylformamide, or a copolymer thereof.

The hygroscopic exothermic polymer is preferably crosslinked.
Further, the hygroscopic exothermic polymer preferably has a specific functional group that exhibits hygroscopicity. Specifically, it preferably has a functional group such as a —COOH group, a —COONa group, a —CONH ₂ group, a —OH group, and an ether bond. Among these, -COOH group, -COONa group, -CONH ₂ group is preferred.

  Further, the exothermic auxiliary agent is not limited as long as it is supported in a state that does not block the pores of silica, for example, in the state of molecules, clusters, particles, or any other state in silica. They may be uniformly dispersed, or they may be attached and adhered to the silica surface. Further, a part of the exothermic aid may be bonded to a silicon atom directly or through oxygen. In particular, from the viewpoint of durability in washing and the like, it is preferable that a part of the heat generation aid is fixed to the pore walls of silica.

  The content of the exothermic auxiliary is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, and usually 80% by weight or less, preferably 60% by weight or less based on the silica of the present invention. More preferably, it is in the range of 50% by weight or less. In addition, when 2 or more types of exothermic auxiliary agents are included, it is made for the sum total of the content rate to be in the said range.

Moreover, the carrying | support method of carrying | supporting exothermic auxiliary | assistant is arbitrary, and it is possible to carry | support by the general introduction method of an auxiliary agent which is mentioned later. However, when a hygroscopic exothermic polymer is used as a heat generation aid, it is usually supported on silica by other methods. The method will be described below.
In the case of using a hygroscopic exothermic polymer as the exothermic auxiliary agent, for example, the hygroscopic exothermic polymer is dissolved in a solvent or heated to a melting point or higher and dissolved and introduced into the pores of silica. Specific examples of the introduction method include an impregnation method and a pore filling method.

  Further, for example, when a hygroscopic exothermic polymer containing acrylic acid as a monomer is used, the acrylic may be immobilized on silica by ion exchange with polyvalent ions after introduction into the pores. By this treatment, it is expected that the end of the ion-exchanged hygroscopic exothermic polymer is bonded to silica and the hygroscopic exothermic polymer is bonded to each other, and prevents the hygroscopic exothermic polymer from flowing out of the pores. be able to.

  Furthermore, as another supporting method, a monomer may be polymerized in the pores of silica so that the hygroscopic exothermic polymer is supported in the pores. In this case, usually, the monomer and the reaction initiator are introduced into the pores, and then the monomer is polymerized inside the pores.

  As a method for polymerizing the monomer in the pores, any means used for radical polymerization can be applied. For example, dry heat treatment, steam treatment, dipping method, cold batch method, microwave treatment, ultraviolet treatment and the like can be mentioned. Here, the microwave treatment is to generate heat by applying a high frequency having a wavelength of 2450 MHz or 920 MHz to an object to be heated. These treatment means may be applied alone, or may be combined with, for example, microwave treatment or ultraviolet treatment during steam treatment or dry heat treatment in order to increase heating efficiency. In addition, since it is difficult for the polymerization to proceed in the presence of oxygen in the air, in the case of dry heat treatment, microwave treatment, ultraviolet treatment, it is preferable to treat in an inert gas atmosphere, even in the case of the cold batch method, It is preferable to seal the inside of the system with a sealing material.

  Among these polymerization methods, steam treatment is preferred from the viewpoint of polymerization efficiency and treatment stability. The steam treatment may be any of normal pressure steam, heated steam, and high pressure steam, but from the viewpoint of cost, normal pressure steam or heated steam is preferable. The steam treatment temperature is usually 80 ° C. or higher, preferably 100 ° C. or higher, and is usually 180 ° C. or lower, preferably 160 ° C. or lower. Furthermore, the steam processing time may be about 1 to 10 minutes.

  In addition, after introducing the monomer into the pores and before starting the polymerization, air drying or preliminary drying with a dryer or the like is also preferably performed.

  Furthermore, when supporting the hygroscopic exothermic polymer by carrying out polymerization in the pores, the divinyl monomer is mixed so that the weight ratio of the water absorbing monomer to the divinyl monomer is 1: 1 to 20: 1, It is preferable to polymerize. Thereby, it becomes possible to improve the durability of the hygroscopic exothermic polymer. Although there is no restriction | limiting in the divinyl monomer used in this case, For example, the thing of Unexamined-Japanese-Patent No. 2002-212880 can be used.

  Further, as other auxiliary agent, for example, a moisture absorption auxiliary agent may be supported. The moisture absorption aid is for inclusion in silica in order to give a highly functional humidity control effect, as long as it has a high affinity for moisture, and various substances belonging to the group of organic compounds, inorganic compounds, metal salts, etc. Can be selected. In addition, a hygroscopic adjuvant may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  When supported on silica, the content of at least one of the substances belonging to such a group is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more. It is desirable to carry it in the range of 80% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less. Moreover, a hygroscopic adjuvant may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  In particular, when the moisture absorption aid is a metal salt and the metal salt is contained in the pores, the moisture absorption aid content is stored in the pores due to moisture absorption at the highest humidity in the use conditions. The content is preferably such that the volume of the aqueous solution of the moisture absorption aid is less than or equal to the total pore volume of silica. This is because metal salts exist in the pores as an aqueous solution under high humidity conditions.

  In other words, if the amount of the aqueous solution consisting of the metal salt and the moisture adsorbed on the metal salt exceeds the pore volume, the aqueous solution overflows from the pores, so that the silica is dried again by dehumidification. In this case, the metal salt contained in the aqueous solution and discharged from the pores is unnecessarily attached to the outside of the pores. As a result, there is a possibility that the moisture absorption characteristics of silica are deteriorated. For this reason, when the content of the metal salt increases, the moisture absorption capacity increases, but there is a possibility that it cannot be used in a high humidity range for the above reasons, and the usable humidity range may have to be limited. .

However, if device-like measures such as providing ancillary equipment are allowed, a static operation can be achieved by creating an operation cycle in which silica is regenerated before the amount of aqueous solution in the pores exceeds the pore volume. It can be used even in a high humidity region that cannot be used on the adsorption data.
Moreover, as said moisture absorption adjuvant, when an alkali metal salt and an alkaline-earth metal salt are made to contain in silica especially, the water vapor adsorption amount by silica will become very high. Alkali metals and alkaline earth metals have a very high affinity with water vapor and lead to enhanced moisture absorption performance, so that they can be used as moisture absorption aids. For this reason, when using a moisture absorption aid, it is preferable to include at least one metal salt in the silica as a moisture absorption aid among the metal salts belonging to the group consisting of alkali metal salts and alkaline earth metal salts. .

Here, any alkali metal salt or alkaline earth metal salt to be contained may be used. However, since the affinity with water vapor is particularly strong, for example, LiF, NaF, KF, CaF ₂ , MgF ₂ , Li ₂ SO ₄ , Na ₂ SO ₄ , K ₂ SO ₄ , CaSO ₄ , MgSO ₄ , LiNO ₃ , NaNO ₃ , KNO ₃ , Ca (NO ₃ ) ₂ , Mg (NO ₃ ) ₂ , NaCl, LiCl, CaCl ₂ , MgCl ₂ , LiBr , LiI, or KBr is preferably at least one selected from two or more. Of these, lithium salts are particularly preferable because of their most excellent hygroscopicity, and lithium chloride is particularly preferable because of its high moisture absorption per unit weight.

  The presence state of the above-mentioned moisture absorption aid is arbitrary, for example, even if it is uniformly dispersed in the form of molecules, clusters, particles, or any other state in silica, or they adhere to and adhere to the silica surface. It may be. Further, at least a part of the moisture absorption aid may be bonded to a silicon atom directly or through oxygen. Furthermore, these moisture absorption aids may be solid or liquid. Further, these moisture absorption aids may be in the form of hydrates, and some of them may be aqueous solutions in the pores.

  Here, when the moisture absorption aid is a metal salt belonging to the group consisting of an alkali metal salt and an alkaline earth metal salt, the content is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight. % Or more, and usually 80% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less. Here, the metal salt belonging to the group consisting of an alkali metal salt and an alkaline earth metal salt is a metal salt belonging to the group consisting of an alkali metal salt and an alkaline earth metal salt contained in the silica of the present invention, In order from the one with the highest content, usually 4 types, preferably 3 types, more preferably 2 types, particularly preferably 1 type. Moreover, when there are two or more metal salts belonging to the group consisting of an alkali metal salt and an alkaline earth metal salt, the total metal salt content is set within the above range.

  By the way, when a moisture absorption aid is contained in the silica of the present invention, the silica of the present invention can support a metal salt in a highly dispersed state compared to conventional silica, and maintains excellent pore characteristics even after support. Is possible. As a result, the supported metal salt can exhibit highly efficient moisture absorption performance close to the theoretical moisture absorption amount. The reason seems to be due to various complex factors, and details are unknown, but are estimated as follows.

  Factor 1: Since the support (silica) has a very high purity and has a uniform structure with little distortion of the bond angle of the siloxane bond, the surface state of the support is homogeneous and the metal salt is specific. Fewer active sites to adsorb. Therefore, in general, the metal salt supported in the pores exists in a solid state under low humidity, but in the silica of the present invention, the metal salt is supported in a highly dispersed (that is, uniformly) in the pores and is high. It has a surface area and can exhibit a high adsorption capacity. On the other hand, in general, the metal salt exists as an aqueous solution in the pores under high humidity, but in the silica of the present invention, as in the case of low humidity, the metal salt is highly dispersed (that is, uniformly) in the pores. Supported. When the metal salt is, for example, a lithium salt, the aqueous solution has a relatively high viscosity. In particular, when the aqueous solution is unevenly supported in the pores, a highly viscous part or a thick part of the liquid film is locally generated. In such high-viscosity locations and thick-film locations, conventional silica has insufficient diffusion rate in the pores of moisture absorbed in the pores (that is, in the lithium salt aqueous solution with high viscosity), All lithium salts in the pores tend to be in a state where they do not effectively contribute to moisture absorption (only some of the lithium salts in the pores contribute to moisture absorption). Since the aqueous solution is uniformly supported in the pores, this is suppressed.

  Factor 2: In the silica of the present invention, the pore size distribution is very sharp (the pore size is uniform), so that the supported salt does not precipitate in the pores under different conditions depending on the pore distribution. It is supported with a uniform particle size. That is, in general, when the pore size distribution is broad (that is, when the pore sizes are not uniform), the amount of the metal salt supported in the pores is uneven. Since the contact efficiency is lowered, it becomes difficult to contribute to moisture absorption, or the moisture absorption speed is lowered, so that a sufficient humidity control function cannot be exhibited. On the other hand, in the silica of the present invention, if the pore diameters are uniform, many metal salts in the pores can be supported with a uniform fine particle size, and the number of coarse particles that hardly contribute to moisture absorption decreases. Therefore, a sufficient humidity control function can be expressed.

  In addition, by supporting an auxiliary agent such as an exothermic auxiliary agent or a humidity adjusting auxiliary agent, the pore diameter of silica changes slightly smaller. For this reason, when supporting the exothermic auxiliary, it is preferable to design the pore diameter before supporting the auxiliary in advance in consideration of the change.

  In addition, as other components that silica may have, simple substances and compounds of useful foreign elements such as 3A group, 4A group and 5A group of the periodic table, and transition metals, etc. may be mentioned. Silica may have a useful different element. In addition, the simple substance and compound of a useful different element may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  When silica has a simple substance or a compound of a useful foreign element as another component, examples of the useful foreign element include an element group consisting of 3A group, 4A group and 5A group of the periodic table, transition metal, etc. Examples include simple substances or compounds of at least one element selected from the group of different elements. Of these, specific examples of preferable ones include group 3A elements such as B, Al, Ga, In, and Tl, group 4A elements such as C, Si, Ge, Sn, and Pb, N, P, As, Sb, and Bi. 5A group atoms, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, lanthanoids, Hf, Ta , W, Re, Os, Ir, Pt, Au, Hg, actinoids, transition metal elements such as Rf, DB, Sg, Bh, Hs, and Mt. Among them, B, Al, Ga, In, Tl, Ge, Sn, Pb, P, As, Sb, Bi, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, lanthanoids, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, and actinides are highly active and useful in various applications. It is preferable from a certain point.

  Among these useful different elements, B, Al, Ga, In, Tl, Fe, Ti, P, W, Mo, Zn and the like are particularly preferable for use as a solid acid catalyst / solid base catalyst. Moreover, W, Mo, Tc, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Ni, Cu, etc. are preferable as a hydrogenation catalyst and a dehydrogenation catalyst use. Further, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ge, Pb and the like are preferable as the oxidation-reduction catalyst application. Further, Ti, Zn, W, Sn, Cd, etc. are preferable for photocatalyst use. Further, Ti, Zr, Cr, Fe, Ge, Sb, Bi, V, Mo, W, Mn, Co, Cu, Sc, Nb and the like are preferable as the polymerization catalyst application.

  However, of course, the use of the elements belonging to the 3A group, the 4A group and the 5A group and the transition metal is not limited to the above-mentioned ones, and other antibacterial agent uses (Ti, Ag, Cu, Zn, etc.), Needless to say, various applications such as water resistance improvement (stability imparting) applications (Zr, Ti, etc.), phosphor applications (rare earths, lanthanoids) and the like can be mentioned.

  Note that the silica of the present invention has simple substances and / or compounds of these useful foreign elements when the useful foreign elements are incorporated and contained in the silica or when supported on the silica surface. Shall be included. Moreover, it is preferable that the useful heteroelement simple substance and / or compound are formed in the particle form. However, the particle diameter is desirably small enough not to block the silica pores.

Moreover, the silica of this invention may have an organic group as another component according to a use. Hereinafter, the organic group possessed by silica is referred to as “useful organic group”, and the silica having useful organic group is hereinafter referred to as “organic group-containing silica”. In addition, a useful organic group may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
Although there is no restriction | limiting in the kind of useful organic group introduce | transduced into an organic group containing silica, For example, what is well-known as an organic group of what is called a silane coupling agent can be selected and used. However, the conditions of particularly useful useful organic groups are as follows.

The useful organic group has usually 1 or more carbon atoms, usually 1000 or less, preferably 500 or less, more preferably 100 or less, and still more preferably 50 or less.
The useful organic group is preferably a monovalent or divalent organic group derived from an aliphatic compound, alicyclic compound, aromatic compound, or aliphatic aromatic compound.

  Furthermore, in the useful organic group, at least a part of hydrogen contained in the organic group may be substituted with an atom or an atomic group. The atom or atomic group substituted for the useful organic group is arbitrary, but examples include atoms and organic functional groups. Specific examples include halogen atoms such as F, Cl, Br, and I, phenyl groups, vinyl groups, and methacryloxy. Group, acryloxy group, styryl group, mercapto group, epoxy group, epoxycyclohexyl group, glycidoxy group, amino group, cyano group, nitro group, sulfonic acid group, carboxy group, hydroxy group, acyl group, alkoxy group, ammonium group, allyl group Group and the like.

  When useful organic groups substituted with these atoms or atomic groups are introduced into silica, functionality based on the characteristics of each functional group of the organic functional group appears. What kind of functional group should be selected? Is greatly dependent on the use of the silica material into which the functional group is introduced.

Furthermore, at least a part of hydrogen of these organic functional groups may be further substituted with various atoms or atomic groups such as O, N, or S. However, the organic functional groups exemplified here are examples of those that are easily introduced into silica, and other organic functional groups having various chemical reactivity and physicochemical functionality may be introduced according to the purpose of use. . Moreover, the atom and atomic group which substitute to a useful organic group may be substituted individually by 1 type, and 2 or more types may be substituted by arbitrary combinations and ratios.
The useful organic group may have various atoms or atomic groups such as O, N, or S as a linking group.

  Furthermore, when a useful organic group is supported on the surface of silica, the surface of silica may be modified. In this case, one of the characteristics obtained by surface modification is an improvement in affinity with an organic substance. In order to acquire this property, for example, as useful organic groups, in addition to alkyl groups having 1 to 50 carbon atoms, vinyl groups, methacryloxy groups, acryloxy groups, styryl groups, mercapto groups, epoxy groups, epoxycyclohexyl groups, glycidoxy It is preferable to use a functional group having high affinity or chemical reactivity with a matrix such as an organic resin. Above all, when a vinyl group, methacryloxy group, acryloxy group, or styryl group is used as a useful organic group, it has a double bond in the functional group, and it is strongly bonded to an organic resin having a double bond by a covalent bond. Therefore, the obtained organic group-containing silica exhibits high structural strength and water resistance. Further, the supported useful organic group is also used as a skeleton of various functional materials.

  The useful organic group may be introduced into the organic group-containing silica in any state. Usually, the useful organic group is directly bonded to the number of silicon atoms corresponding to the valence by a covalent bond, and thus the useful organic group is contained in the organic group-containing silica. In this case, since the silicon atom bonded to the useful organic group is a part of what forms the silica skeleton, the useful organic group is substantially directly introduced into the silica skeleton. When a useful organic group is introduced into the silica of the present invention in such a state, a reagent in which a reactive terminal capable of forming a siloxane bond is introduced into the useful organic group may be used. The most readily available and typical examples of such reagents are the silane coupling agents shown below. In addition, there are several general synthetic reagents that react with silanol to form siloxane bonds (hereinafter referred to as “organic group introduction reagents” as appropriate). However, industrial availability is not easy, and the reaction conditions are limited. There are often.

  In this specification, the silane coupling agent is a general term for those in which a useful organic group as described above is directly bonded to a silicon atom, and is a compound represented by the following formulas (I) to (IV).

X ₃ SiR ¹ Formula (I)
In the formula (I), each X independently represents a hydrolyzable silyl group that is hydrolyzed with water in the aqueous solution, in the air, or with water adsorbed on the inorganic surface to form a highly reactive silanol group. Represent. There is no restriction | limiting in the specific kind, A conventionally well-known thing can be used arbitrarily. Examples thereof include a lower alkoxy group having 1 to 4 carbon atoms, an acetoxy group, a butanoxime group, a chloro group and the like. In addition, these hydrolysable silyl groups may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
R ¹ represents a monovalent group of the above useful organic groups.

  Silane coupling agents represented by the formula (I) are the most versatile. Specific examples thereof include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, p-aminophenyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, aminoethylamino Methylphenethyltrimethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrichlorosilane, (p-chloromethyl) phenyltrimethoxysilane, 4-chlorophenyltri Meto Sisilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, styrylethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltri Examples include ethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, and trifluoropropyltrimethoxysilane.

X ₂ SiR ² R ³ Formula (II)
In formula (II), each X independently represents a hydrolyzable silyl group similar to X in formula (I).
R ² and R ³ each represent a monovalent useful organic group as in R ^{1 of} formula (I). R ² and R ³ may be the same group or different groups.

  Specific examples of the silane coupling agent represented by the formula (II) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane and the like.

XSiR ⁴ R ⁵ R ⁶ Formula (III)
In the formula (III), X represents a hydrolyzable silyl group similar to X in the formula (I).
R ⁴ , R ⁵ , and R ⁶ each represent a monovalent useful organic group, similarly to R ^{1 in the} formula (I). R ⁴ , R ⁵ and R ⁶ may be the same group or different groups.
Specific examples of the silane coupling agent represented by the formula (III) include trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, triphenylchlorosilane and the like.

(X ₃ Si) _m R ⁷ Formula (IV)
In formula (IV), each X independently represents a hydrolyzable silyl group similar to X in formula (I).
R ⁷ represents an m-valent useful organic group. M represents an integer of 2 or more.
Specific examples of the silane coupling agent represented by the formula (IV) include those in which a plurality of hydrolyzable silyl groups are bonded as side chains to various organic polymers and oligomers.

The compounds specifically exemplified in these formulas (I) to (IV) are some of the commercially available silane coupling agents that are readily available. It can be shown by the list of coupling agents and related products in Chapter 9 “Technology for Use”.
Naturally, the silane coupling agent that can be used in the present invention is not limited by these examples.

The kind and amount of the useful organic group to be introduced are not particularly limited as long as the useful organic group exhibits a functionality. Therefore, any silane coupling agent or organic group introduction reagent having these useful organic groups may be used. From the viewpoint of obtaining high-purity organic group-containing silica, it is preferable to use a high-purity silane coupling agent or organic group-introducing reagent containing a useful organic group.
In addition to the useful different elements and useful organic groups described above, other components that silica may have may be used alone or in combination of two or more in any combination and ratio. Also good.

[1-2] Method for producing silica of the present invention:
Then, the manufacturing method of the silica of this invention is demonstrated.
The method for producing the silica of the present invention is not particularly limited, and can be produced by any known method. Examples of methods often used as a method for producing silica include the following methods.
i. A method of gelling after neutralizing water glass with an acid such as sulfuric acid.
ii. A method in which alkoxysilane is hydrolyzed and then gelled.
iii. A method of forming pores using alkoxysilane or water glass as a raw material and using a surfactant as an organic template (so-called micelle template silica).

As described above, the method for producing the silica of the present invention is not particularly limited, but preferably, the silica of the present invention is preferably produced by the method described below.
That is, the silica of the present invention is preferably produced by subjecting silica hydrogel to hydrothermal treatment, and setting the water content in the liquid component of the resulting slurry to, for example, 5% by weight or less, followed by drying.

  Specifically, the silicon alkoxide is hydrolyzed, and the obtained silica hydrogel is preferably hydrothermally treated without substantially aging to remove moisture in the silica. In addition, the process of making it contact with a hydrophilic organic solvent after hydrothermal treatment may be included.

  The manufacturing method of silica hydrogel is arbitrary, for example, the silica hydrogel obtained by hydrolyzing a silicic acid alkali salt, or the silica hydrogel obtained by hydrolyzing a silicon alkoxide is mentioned. Among them, silica hydrogel obtained by hydrolyzing silicon alkoxide is preferable because it can increase the purity of silicon alkoxide as a raw material and can easily prevent impurities from being mixed into silica hydrogel.

  The silicon alkoxide used as a raw material for the silica of the present invention includes a lower alkyl group having 1 to 4 carbon atoms such as trimethoxysilane, tetramethoxysilane, triethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like. Examples thereof include tri- or tetraalkoxysilanes or oligomers thereof. Among these, tetramethoxysilane, tetraethoxysilane and oligomers thereof, particularly tetramethoxysilane and oligomers thereof are preferable because silica having good pore characteristics can be obtained. The main reason is that silicon alkoxide is easily purified by distillation to obtain a high-purity product, and is therefore suitable as a raw material for high-purity silica. The total content of metal elements (metal impurities) belonging to the alkali metal or alkaline earth metal in the silicon alkoxide is usually 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less, and particularly preferably 1 ppm or less. The content of these metal impurities can be measured by the same method as the method for measuring the impurity content in general silica.

  In the present invention, first, in the hydrolysis / condensation step, the silicon alkoxide is hydrolyzed in the absence of a catalyst and the silica hydrosol obtained is condensed to form a silica hydrogel.

  The amount of water used for the hydrolysis of the silicon alkoxide is arbitrary, but usually 2 mol times or more, preferably 3 mol times or more, particularly preferably 4 mol times or more, and usually 20 mols per mol of silicon alkoxide. Double or less, preferably 10 mol times or less, particularly preferably 8 mol times or less of water is used. Hydrolysis of the silicon alkoxide produces a silica hydrogel and an alcohol, and the produced silica hydrosol is successively condensed into a silica hydrogel.

  The temperature at the time of hydrolysis is arbitrary, but it is usually room temperature or higher and 100 ° C. or lower. However, it can be performed at a higher temperature by maintaining the liquid phase under pressure. The reaction time required for hydrolysis depends on the composition of the reaction solution (type of silicon alkoxide and molar ratio with water) and the reaction temperature, and since the time until gelation differs, it is not generally specified. This reaction time is preferably a time at which the fracture stress of the hydrogel does not exceed 6 MPa in order to obtain a silica having excellent pore characteristics such as the silica of the present invention.

  In this hydrolysis reaction system, hydrolysis can be promoted by allowing an acid, an alkali, a salt, or the like to coexist as a catalyst. However, the use of such a catalyst is not so preferable in the production of the silica of the present invention because it causes aging of the produced hydrogel, as will be described later.

  In the hydrolysis of the above-mentioned silicon alkoxide, it is important to sufficiently stir. For example, when a stirrer equipped with a stirring blade on the rotating shaft is used, the stirring speed (the number of rotations of the rotating shaft) depends on the shape, the number of the stirring blades, the contact area with the liquid, etc. 30 rpm or more, preferably 50 rpm or more.

  In general, if the stirring speed is too high, droplets generated in the tank block various gas lines or adhere to the inner wall of the reactor to deteriorate the heat conduction, which is an important temperature control property. It may affect management. Furthermore, the deposits on the inner wall may be peeled off and mixed into the product to deteriorate the quality. For these reasons, the stirring speed is preferably 2000 rpm or less, and more preferably 1000 rpm or less.

  In the present invention, any stirring method can be used as the stirring method for the two liquid phases (aqueous phase and silicon alkoxide phase) which are separated, as long as the method promotes the reaction. Among them, examples of an apparatus for further mixing the two liquid phases include the following (A) and (B).

(A): An apparatus having a stirring blade in which a rotating shaft is inserted perpendicularly or slightly at an angle with respect to the liquid surface, and the liquid flows vertically.
(B): A stirrer having a stirring blade provided with a rotation axis direction substantially parallel to the interface between the two liquid phases and causing stirring between the two liquid phases.

  The rotational speed of the stirring blade when using the devices such as (A) and (B) described above is usually 0.05 m / s or more, preferably 0. It is preferably 1 m / s or more, usually 10 m / s or less, preferably 5 m / s or less, and more preferably 3 m / s or less.

  The shape and length of the stirring blade is arbitrary, and examples of the stirring blade include a propeller type, a flat blade type, an angled flat blade type, a pitched flat blade type, a flat blade disk turbine type, a curved blade type, a fiddler type, Examples include a bull margin type.

  The width, number of blades, inclination angle, etc. of the blades may be appropriately selected according to the shape and size of the reactor and the target stirring power. For example, the ratio (b / D) of the blade width (blade length in the rotation axis direction) to the tank inner diameter (the longest diameter of the liquid phase surface forming a plane perpendicular to the rotation axis direction) of the reactor is 0.05 to A suitable example is 0.2, an inclination angle (θ) of 90 ° ± 10 °, and a stirring device of 3 to 10 blades.

  Among these, the structure in which the above-described rotating shaft is provided above the liquid level in the reaction vessel and the stirring blade is provided at the tip of the shaft extending from the rotating shaft is preferably used from the viewpoint of stirring efficiency and equipment maintenance. .

  In the above silicon alkoxide hydrolysis reaction, the silicon alkoxide is hydrolyzed to form a silica hydrosol. Subsequently, a condensation reaction of the silica hydrosol occurs, the viscosity of the reaction solution increases, and finally gelation occurs. Silica hydrogel.

  Next, in the present invention, as a physical property adjusting step, hydrothermal treatment of the silica hydrogel is performed without substantially aging so that the hardness of the silica hydrogel generated by the above hydrolysis does not increase. Hydrolysis of silicon alkoxide produces a soft silica hydrogel. In order to stabilize the physical properties of the hydrogel, it is usually difficult to produce the silica of the present invention by a method of aging or drying, followed by hydrothermal treatment.

  The hydrothermal treatment immediately performed without substantially aging the silica hydrogel produced by hydrolysis as described above means that the next hydrothermal treatment is performed while maintaining the soft state immediately after the silica hydrogel is produced. It means to be used for.

  Specifically, it is preferable that the hydrothermal treatment is generally performed within 10 hours from the time when the silica hydrogel is formed, and the hydrothermal treatment is preferably performed within 8 hours, more preferably within 6 hours, particularly within 4 hours. It is preferable.

  Moreover, in an industrial plant etc., the case where the silica hydrogel produced | generated in large quantities is once stored in a silo etc. and hydrothermal treatment is performed after that can be considered. In such a case, the time from when the silica hydrogel is formed to when it is subjected to hydrothermal treatment, the so-called standing time, may exceed the above range. In such a case, for example, the liquid component in the silica hydrogel may be prevented from drying during standing in the silo so that aging does not substantially occur.

  Specifically, for example, the inside of the silo may be sealed or the humidity may be adjusted. Alternatively, the silica hydrogel may be allowed to stand in a state where the silica hydrogel is immersed in water or another solvent.

  The temperature at the time of standing is preferably as low as possible, for example, 50 ° C. or less, particularly 35 ° C. or less, particularly preferably 30 ° C. or less. Further, as another method for preventing aging substantially from occurring, there is a method of preparing a silica hydrogel by controlling the raw material composition in advance so that the silica concentration in the silica hydrogel is lowered.

  Considering the effect obtained by hydrothermal treatment without substantially aging the silica hydrogel and the reason why this effect is obtained, the following can be considered.

  First, when the silica hydrogel is aged, a macroscopic network structure due to —Si—O—Si— bonds is considered to be formed in the entire silica hydrogel. It is considered that this network structure is present in the entire silica hydrogel, so that this network structure becomes an obstacle during hydrothermal treatment, and it becomes difficult to form mesoporous materials. Moreover, the silica hydrogel obtained by previously controlling the raw material composition so that the silica concentration in the silica hydrogel is low can suppress the progress of crosslinking in the silica hydrogel that occurs during standing. Therefore, it is considered that the silica hydrogel does not age.

  Therefore, in this silica production method, it is important to perform hydrothermal treatment without aging the silica hydrogel.

  Mixing an acid, alkali, salt or the like into the silicon alkoxide hydrolysis reaction system or making the temperature of the hydrolysis reaction too strict is not preferable from the viewpoint of aging the hydrogel. Also, temperature and time should not be taken more than necessary in washing, drying, leaving, etc. in post-treatment after hydrolysis.

  Further, the silica hydrogel obtained by hydrolysis of silicon alkoxide is pulverized before hydrothermal treatment so that the average particle size is 10 mm or less, especially 5 mm or less, more preferably 1 mm or less, particularly 0.5 mm or less. Etc. are preferably applied.

  As described above, in the method for producing silica of the present invention, a method of immediately hydrothermally treating the silica hydrogel immediately after the production of the silica hydrogel is important. However, in the method for producing silica according to the present invention, it is sufficient that the hydrothermally treated silica hydrogel is not matured. For example, the hydrothermal treatment is performed after standing at a low temperature for a while, and the silica hydrogel is not necessarily immediately produced. There is no need to immediately hydrotreat it.

  As described above, when the hydrothermal treatment is not performed immediately after the formation of the silica hydrogel, the hydrothermal treatment may be performed after specifically confirming the aging state of the silica hydrogel. The means for specifically confirming the ripening state of the hydrogel is arbitrary, and examples thereof include a method referring to the hardness of the hydrogel. That is, as described above, silica having a physical property range defined in the present invention can be obtained by hydrothermally treating a soft hydrogel having a fracture stress of usually 6 MPa or less. The fracture stress is preferably 3 MPa or less, and particularly preferably 2 MPa or less.

  The conditions for this hydrothermal treatment are arbitrary, and the water state may be either liquid or gas. Among these, it is preferable to use liquid water and perform hydrothermal treatment as a slurry in addition to silica hydrogel. In the hydrothermal treatment, first, the silica hydrogel to be treated is usually at least 0.1 times by weight, preferably at least 0.5 times by weight, particularly preferably at least 1 times by weight, more usually at least 1 time by weight relative to the weight of the silica hydrogel. 10 weight times or less, preferably 5 weight times or less, particularly preferably 3 weight times or less of water is added to form a slurry. The slurry is usually 30 ° C. or higher, preferably 40 ° C. or higher, more preferably 100 ° C. or higher, more preferably 150 ° C. or higher, particularly preferably 170 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower. Hydrothermal treatment is performed at a temperature of usually 0.1 hour or longer, preferably 1 hour or longer, and usually 100 hours or shorter, preferably 10 hours or shorter. If the temperature of the hydrothermal treatment is too low, the pore distribution is difficult to be sharp, and it may be difficult to increase the pore volume.

  Note that the water used for the hydrothermal treatment may contain a solvent. Specific examples of the solvent include lower alcohols such as methanol, ethanol, and propanol. This solvent may be alcohols derived from alkoxysilane, which is a raw material, when hydrothermally treating a silica hydrogel obtained by hydrolyzing alkoxysilane, for example.

  The content of such a solvent in the water used for the heat treatment is arbitrary, but it is preferably smaller. For example, when hydrotreating a silica hydrogel obtained by hydrolyzing an alkoxysilane as described above, the silica hydrogel is washed with water, and the washed water is subjected to a hydrothermal reaction. Even when hydrothermal treatment is performed with the temperature lowered to 1, silica having excellent pore characteristics and a large pore volume can be produced. Even if hydrothermal treatment is performed with water containing a solvent, the silica of the present invention can be easily obtained by performing hydrothermal treatment at a temperature of about 200 ° C.

  Further, this hydrothermal treatment method is also applied when silica is formed in a film or layer form on a substrate such as a particle, a substrate, or a tube for the purpose of making a membrane reactor or the like. It is also possible to perform hydrothermal treatment by changing the temperature conditions using a hydrolysis reaction reactor, but the optimum conditions are usually different between the hydrolysis reaction and the subsequent hydrothermal treatment. In general, it is difficult to obtain the silica of the present invention by a method carried out without newly adding water.

  In the above hydrothermal treatment conditions, when the temperature is increased, the diameter and pore volume of the resulting silica tend to increase. Further, with the treatment time, the specific surface area of the obtained silica tends to gradually decrease after reaching a maximum once. Based on the above tendency, it is necessary to appropriately select conditions according to desired physical property values. For example, when attention is paid to humidity control performance, the hydrothermal treatment temperature is preferably in the range of 100 ° C. to 200 ° C. in the case of producing silica exhibiting high humidity control performance. Since the hydrothermal treatment is intended to change the physical properties of silica, it is usually preferable to use a higher temperature condition than the hydrolysis reaction conditions.

  In order to produce silica having excellent microstructural homogeneity, it is necessary to set fast heating rate conditions so that the temperature in the reaction system reaches the target temperature within 5 hours during hydrothermal treatment. preferable. Specifically, when the tank is filled and processed, the average rate of temperature increase from the start of temperature increase until reaching the target temperature is usually 0.1 ° C./min or more, preferably 0.2 ° C./min or more. Usually, it is preferable to employ a value in the range of 100 ° C./min or less, preferably 30 ° C./min or less, more preferably 10 ° C./min or less.

  A temperature raising method using a heat exchanger or the like or a temperature raising method in which hot water prepared in advance is used is preferable because the temperature raising rate can be shortened. Moreover, if the temperature increase rate is in the above range, the temperature may be increased stepwise. When it takes a long time for the temperature in the reaction system to reach the target temperature, the aging of the silica hydrogel progresses during the temperature rise, and the microstructural homogeneity may be lowered.

  The temperature raising time until the above target temperature is reached is preferably within 4 hours, more preferably within 3 hours. In order to shorten the temperature raising time, the water used for the hydrothermal treatment can be preheated.

If the hydrothermal treatment temperature and time are set outside the above ranges, it may be difficult to obtain the silica of the present invention. For example, if the hydrothermal treatment temperature is too high, the pore diameter and pore volume of silica become too large, and the pore distribution is also widened. On the other hand, if the hydrothermal treatment temperature is too low, the resulting silica has a low degree of crosslinking, poor thermal stability, no peaks in the pore distribution, or Q ⁴ / Q ³ value may become extremely small.

  When the hydrothermal treatment is performed in ammonia water, the same effect can be obtained at a lower temperature than in pure water. In addition, when hydrothermal treatment is performed in ammonia water, the finally obtained silica generally becomes hydrophobic as compared with hydrothermal treatment using water not containing ammonia. At this time, when the temperature of the hydrothermal treatment is usually 30 ° C. or higher, preferably 40 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower, the hydrophobicity is particularly high. The ammonia concentration here is preferably 0.001% by weight or more, particularly preferably 0.005% by weight or more, and preferably 10% by weight or less, particularly preferably 5% by weight or less.

  The resulting silica of the present invention is dried under suitable conditions. The drying condition is arbitrary, but it is usually 40 ° C. or higher, preferably 60 ° C. or higher, and usually 200 ° C. or lower, preferably 120 ° C. or lower. The drying method is not particularly limited, and it may be a batch type or a continuous type, and can be dried under normal pressure or reduced pressure. Among these, vacuum drying is preferable because not only can drying be performed quickly, but also the pore volume and specific surface area of the resulting silica are increased.

If necessary, if carbon content derived from the raw material silicon alkoxide is contained, it can be usually removed by firing at 400 ° C. to 600 ° C. Moreover, in order to control a surface state, it may bake at the temperature of a maximum of 900 degreeC. Furthermore, a surface treatment for adjusting hydrophilicity / hydrophobicity may be performed with a silane coupling agent, an inorganic salt, various organic compounds, or the like. In addition, although the kind of silane coupling agent used by this surface treatment is arbitrary, the thing similar to the silane coupling agent mentioned above can be used as what is used for useful organic group introduction | transduction, for example.
Furthermore, the silica of the present invention, which is the final object, is obtained by pulverizing and classifying the obtained silica as necessary.

  In addition, it is preferable to perform drying after substituting the water contained in a silica with a hydrophilic organic solvent after said hydrothermal treatment. As a result, silica shrinkage in the drying process can be suppressed, the silica pore volume can be maintained large, and silica having excellent pore characteristics and a large pore volume can be obtained. The reason for this is not clear, but is thought to be due to the following phenomenon.

  Many of the liquid components in the silica slurry after the hydrothermal treatment are water. Since this water interacts strongly with silica, it is considered that a large amount of energy is required to completely remove the water from the silica.

  When a drying process (for example, heat drying) is performed under a condition where a large amount of water is present, water that has received heat energy reacts with unreacted silanol groups, and the structure of the silica of the present invention changes. Among the structural changes, the most prominent change is the condensation of the silica skeleton, and it is considered that the silica is locally densified by the condensation. Since the silica skeleton has a three-dimensional structure, local condensation of the skeleton (densification of the silica skeleton) affects the pore characteristics of the entire silica particles composed of the silica skeleton, and as a result, the particles It is considered that the pore volume and the pore diameter shrink due to the shrinkage.

  Therefore, for example, by replacing the liquid component (containing a large amount of water) in the silica slurry with a hydrophilic organic solvent, it is possible to remove the water in the silica slurry and suppress the silica shrinkage as described above. Become.

  The hydrophilic organic solvent used here should just be what dissolves much water based on the idea mentioned above. Among them, those having large intramolecular polarization are preferable. More preferably, the relative dielectric constant is 15 or more.

  Further, in the above-described method for producing silica of the present invention, in order to obtain high-purity silica, the hydrophilic organic solvent is used in a drying step after removing water with the hydrophilic organic solvent. Need to be removed. Therefore, as the hydrophilic organic solvent, those having a low boiling point that can be easily removed by drying (for example, heat drying, vacuum / vacuum drying, etc.) are preferable. The boiling point of the hydrophilic organic solvent is usually 150 ° C. or lower, preferably 120 ° C. or lower, particularly preferably 100 ° C. or lower.

  Specific hydrophilic organic solvents include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone and diethyl ketone, nitriles such as acetonitrile, amides such as formamide and dimethylformamide, and aldehydes And ethers. Among these, alcohols and ketones are preferable, and lower alcohols such as methanol, ethanol, and propanol, and acetone are particularly preferable. In producing the silica of the present invention, one of these exemplified hydrophilic organic solvents may be used alone, or two or more of them may be used in combination in any combination and in any ratio.

  If water can be removed, the hydrophilic organic solvent to be used may contain water. Of course, the water content in the hydrophilic organic solvent is preferably as low as possible, and is usually 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.

  In the production of the silica of the present invention, the temperature and pressure during the substitution treatment with the above-mentioned hydrophilic organic solvent are arbitrary. The treatment temperature is arbitrary, but is usually 0 ° C. or higher, preferably 10 ° C. or higher, usually 100 ° C. or lower, and preferably 60 ° C. or lower. The pressure during the treatment may be normal pressure, pressurization, or reduced pressure.

  The amount of the hydrophilic organic solvent brought into contact with the silica slurry is also arbitrary. However, if the amount of the hydrophilic organic solvent used is too small, the rate of progress of the substitution with water is not sufficient, and conversely if too large, the substitution efficiency with water increases, but there is an effect commensurate with the increase in the amount of use of the hydrophilic organic solvent. This is not economically favorable. Therefore, the amount of the hydrophilic organic solvent to be used is usually 0.5 to 10 times the volume of the bulk volume of silica. This replacement operation with a hydrophilic organic solvent is preferably repeated a plurality of times because water replacement is more reliable.

  The contact method of the hydrophilic organic solvent and the silica slurry is arbitrary, for example, a method of adding the hydrophilic organic solvent while stirring the silica slurry in a stirring tank, or packing the silica separated from the silica slurry into a packed tower, Examples thereof include a method in which a hydrophilic organic solvent is passed through the packed tower, a method in which silica is immersed in a hydrophilic organic solvent, and a method of allowing to stand.

  The completion of the replacement operation with the hydrophilic organic solvent may be determined by measuring the moisture in the liquid component of the silica slurry. For example, the silica slurry is periodically sampled to measure the water content, and the end point may be that the water content is usually 5% by weight or less, preferably 4% by weight or less, more preferably 3% by weight or less. . The method for measuring moisture is arbitrary, and for example, the Karl Fischer method can be mentioned.

  After the substitution operation with the hydrophilic organic solvent, the silica of the present invention can be produced by separating the silica and the hydrophilic organic solvent and drying. As the separation method at this time, any conventionally known solid-liquid separation method may be used. That is, solid-liquid separation may be performed by selecting a method such as decantation, centrifugation, and filtration according to the size of the silica particles. One of these separation methods may be used alone, or two or more may be used in any combination.

  Incidentally, as described above, the produced silica is usually granulated by pulverization, classification, etc., and used as particulate silica. The shape of the silica particles produced at this time is not limited and is arbitrary. For example, it may be spherical, may be other lumps whose shape is not specified, or may be crushed into a fine shape ( It may be a crushed form, or may be a crushed form collected and granulated. In terms of cost, a crushed shape in which the particle size is easily controlled or a granulated product thereof is preferable. Further, silica may be formed into a honeycomb shape. The particle size of silica is appropriately set depending on the use conditions.

Furthermore, the method of pulverizing and classifying silica is arbitrary.
As a specific example, the classification of silica is performed using, for example, a sieve, a gravity classifier, a centrifugal classifier or the like.
Silica is pulverized by, for example, a ball mill (rolling mill, vibrating ball mill, planetary mill, etc.), agitation mill (tower crusher, agitation tank type mill, flow tube type mill, annular (annular) mill, etc.), high speed Rotary pulverizer (screen mill, turbo type mill, centrifugal classification type mill), jet pulverizer (circulation jet mill, collision type mill, fluidized bed jet mill), shear mill (disintegrator, ong mill), colloid mill, mortar Such devices and instruments can be used. Among these, when the silica has a relatively small diameter (for example, 2 μm or less), a ball mill and a stirring mill are more preferable. Moreover, as the state at the time of pulverization, there are a wet method and a dry method, both of which can be selected, but when the silica is made to have a relatively small diameter, the wet method is more preferable. In the case of the wet method, the dispersion medium to be used may be any of organic solvents such as water and alcohol, or may be a mixed solvent of two or more types, and is used properly according to the purpose. It is not preferable to apply an unnecessarily strong pressure or shear force for a long time at the time of fine pulverization because the pore characteristics of silica may be impaired.

Furthermore, when producing silica for fiber use among wet pulverization, it is preferable to reduce the bead diameter used for pulverization. Specifically, the bead diameter is usually 0.5 mm or less, preferably 0.3 mm or less. Thereby, the particle diameter of silica for fiber use (that is, silica fixed to the fiber by a binder resin in order to produce a molded body using fiber as a base material) is in a suitable range {the above-mentioned condition (i) } Can be easily stored.
Further, it is preferable that the pulverizer has a higher bead efficiency (a pulverization amount per bead).

  In addition, when the silica produced as described above is pulverized or the like to form particles, the pulverized silica particles (primary particles) are granulated by a known method, and granular (for example, spherical) or It is good also as the shape of an aggregate. Silica generally has a primary particle size of 2 μm or less, and it is possible to obtain agglomerated particles simply by drying it as a water slurry without mixing a binder resin. In the case of particles exceeding 2 μm, Often a binder is required. The aggregate when the binder resin is mixed is composed of silica and binder resin, and if 30% or more of the pore volume is open to the outside, it corresponds to the molded body of the present invention.

  The substance that can be used as the binder resin in the production of the agglomerated particles is arbitrary, but when dissolved in water, for example, sugar, dextrose, corn syrup, gelatin, carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), Other water-soluble polymers, water glass, silicon alkoxide hydrolyzate (which can also be used in solvent systems), etc. can be used. When dissolved in a solvent, various waxes, lacquers, syrac, oil-soluble A polymer or the like can be used. In addition, the binder resin used in this case may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios. However, in order to obtain an agglomerate without impairing the porous performance of silica, it is desirable not to use a binder resin, and when it is unavoidably used, the minimum use amount is used to induce a change in the physical properties of silica. It is preferable to use a high-purity one with a small amount of metal impurities.

By the way, as described above, any known method may be used as the silica granulation method (pulverization method), but as a representative method, a rolling method, a fluidized bed method, a stirring method, a crushing method, a compression method are used. Method, extrusion method, injection method and the like. Among these, in order to obtain silica particles with controlled pore characteristics of the present invention, pay attention to the selection of the type, amount and purity of the binder resin, and do not apply unnecessary pressure when granulating silica. That is important.
In the above, specific examples of the method for producing silica according to the present invention have been described. However, the method for producing the silica should be substantially limited except that the silica hydrogel is not aged before hydrothermal treatment for pore control. is not.

  Incidentally, as described above, the silica of the present invention can contain other components. A specific method for adding other components to silica is arbitrary.

  For example, when the auxiliary agent is introduced into silica, the following introduction method can be used. That is, when producing the silica of the present invention by doping an auxiliary agent before hydrothermal treatment, it is mixed with the auxiliary agent after hydrolyzing the raw material alkali silicate or silicon alkoxide and before gelling it. And the silica of this invention containing an auxiliary agent can be manufactured by performing hydrothermal treatment to the silica hydrogel obtained by this. As an application example, it is preferable that hydrothermal treatment may be performed after mixing and hydrolyzing silicon alkoxide and an auxiliary agent.

  In the process of hydrolyzing the silicon alkoxide to obtain a silica hydrogel, one or more auxiliary agents are mixed in the system. About the form etc., if it is a range which does not prevent formation of a homogeneous silica hydrogel, it will not specifically limit, The thing which does not express strong catalytic activity with respect to a hydrolysis of a silicon alkoxide is preferable. Further, from the viewpoint of obtaining high-purity silica, it is preferable to use a high-purity auxiliary agent.

  The method of mixing the auxiliary agent is not particularly limited as long as it does not prevent the formation of a homogeneous silica hydrogel. The auxiliary agent may be mixed with water for silicon alkoxide hydrolysis or mixed with silicon alkoxide, It may be mixed with a hydrosol that has become a homogeneous solution immediately after hydrolysis, and is appropriately selected according to operability. Further, if necessary, the auxiliary agent may be mixed with the above-mentioned system after hydrolysis in advance, or conversely, the auxiliary agent may be mixed after partial hydrolysis of the silicon alkoxide.

  The silica of the present invention can also be produced by a method in which an auxiliary agent is post-supported on high-purity silica after pore control. In this case, first, an auxiliary agent is introduced into the silica pores. As the method, any known method may be used. For example, an impregnation method well known as a catalyst preparation method may be mentioned. Specific examples include an absorption method, a pore-filling method, an “incipient wetness” method, an evaporation to dryness method, a spray method, and a dry concentrate method. . However, when a moisture absorption aid is supported as an auxiliary agent, if the moisture absorption aid adheres to the outside of the pores, the moisture absorption aid becomes large particles and the moisture absorption characteristics are deteriorated. A method in which the aqueous solution does not overflow outside the pores is preferred.

  Furthermore, in this case as well, the auxiliary agent can be supported on the silica obtained by hydrothermal treatment without hydrolyzing and aging the silicon alkoxide by the above method. If it is a range which expresses functionality, it will not specifically limit. Further, from the viewpoint of obtaining high-purity silica, it is preferable to use a high-purity auxiliary agent.

  Moreover, you may perform the surface treatment for changing states, such as hydrophilicity / hydrophobicity of the silica surface which is a support | carrier, surface activity, and acidity as needed. Although any of the above-mentioned methods may be used for the inclusion of the auxiliary agent, the method by loading is more preferable because the pore control can be performed reliably and the auxiliary agent to be contained can be selected widely.

Needless to say, the method described here can also be applied to the heat generation aid and the moisture absorption aid.
In addition, in the case of containing and / or supporting a simple substance or compound of a useful foreign element as another component on silica, a method similar to the above-described method for introducing an auxiliary agent can be used.

Further, when a useful organic group is introduced into silica as another component, for example, in the method for introducing an auxiliary agent described above, the same operation is performed except that a silica coupling agent (or an organic group introducing reagent) is used instead of the auxiliary agent. In this way, useful organic groups can be introduced.
That is, when the auxiliary agent is introduced into silica, when the silicon alkoxide is hydrolyzed, the above-described silane coupling agent (or organic group introduction reagent) containing a useful organic group is mixed before gelation. Subsequently, using the silica hydrogel obtained in this manner, an organic group-containing silica can be produced by applying a hydrothermal treatment method.
Moreover, as this application example, preferably, a method in which silicon alkoxide is mixed with a silane coupling agent or an organic group introduction reagent and then hydrolyzed. In this step, it is difficult to use an organic group introduction reagent that is deactivated by moisture.

  Furthermore, the silane coupling agent and the organic group introduction reagent are mixed in the system in the process of hydrolyzing silicon aldehyde to obtain silica hydrogel. The type and amount of the organic group introduction reagent are not particularly limited as long as they do not interfere with the formation of a homogeneous silica hydrogel as described above, and these silane coupling agents and organic group introduction reagents are those reagents. Any kind of product may be used as long as it does not interfere with the formation of a homogeneous hydrogel by itself or a decomposition product accompanying the reaction. Further, from the viewpoint of obtaining high-purity silica gel, it is preferable to use high-purity silane coupling agents and organic group introduction reagents.

  The method for mixing the silane coupling agent and the organic group introduction reagent is not particularly limited as long as it does not prevent the formation of a homogeneous silica hydrogel, and the silane coupling agent and the organic group introduction reagent are used for hydrolysis of silicon alkoxide. It may be mixed with water, mixed with silicon alkoxide, or mixed with a hydrosol that has become a homogeneous solution immediately after hydrolysis, and is appropriately selected according to operability. Further, if necessary, the silane coupling agent or organic group introduction reagent is hydrolyzed in advance and then mixed into the above system, or conversely, after partial hydrolysis of silicon alkoxide, the silane coupling agent or organic group is mixed. An introduction reagent may be mixed.

  Furthermore, the organic group-containing silica can also be produced by a method of post-supporting a target compound containing useful organic groups on high-purity silica after pore control. In this case, first, a silane coupling agent or an organic group introduction reagent is introduced into the pores of silica. As the method, for example, wet processing methods (aqueous solvent system, non-aqueous solvent system) well known as silane coupling agent processing methods for inorganic powders, dry processing methods, slurry methods, spray methods, dry concentrates. Any known method such as a method may be used.

  As described above, useful organic groups can be introduced into the silica gel obtained by hydrothermal treatment without hydrolyzing and aging the silicon alkoxide by the above method, but the target organic group is post-supported. In some cases, pretreatment may be performed on the high-purity silica gel used as the carrier. For example, you may perform the baking removal of the carbon content derived from the raw material mentioned above, the baking for controlling a surface state, the boiling process by an inorganic acid, etc.

[1-3] Characteristics of the silica of the present invention:
The silica of the present invention has a controlled structure so as to have a large pore volume and specific surface area. Therefore, the adsorption exothermic property, humidity control property, moisture absorption exothermic property, drug sustained release property, adsorptive property, and Absorption and release performance such as antibacterial properties can be exhibited effectively. Moreover, the target characteristic can be further enhanced by using an auxiliary agent such as the above-described exothermic auxiliary agent and moisture absorption auxiliary agent.

In particular, the silica of the present invention has an excellent humidity control function for the following reasons.
Silica absorbs excess water vapor at high humidity, but releases water vapor that has been absorbed at low humidity. If the average pore size is set to 3-5 nm, the system is comfortable corresponding to the average pore size. Humidity can be adjusted to a low humidity (40% to 60%). In addition, if the average pore size is set to 5 nm to 10 nm, moisture in the high humidity (60% to 90%) is absorbed to adjust the humidity. For example, stuffiness under high humidity such as after exercise in clothes is eliminated. can do. This humidity control function is evaluated by the adsorption isotherm of water vapor on silica. The sharper the pore size distribution, the more rapidly the moisture adsorption near the relative humidity corresponding to the most frequent pore diameter. The amount (moisture absorption capacity) tends to increase. However, in the conventional silica, since the pore size distribution is broad, the change in the amount of adsorption of water vapor with respect to the change in humidity becomes slow, and the humidity adjustment becomes slow.

Relative vapor pressure (P / P ₀ ) where the adsorbed substance (here, water vapor) starts capillary condensation and is suddenly adsorbed on silica [here, since the adsorbed substance is water vapor, (P / P ₀ × 100) is relative humidity ( %) And the pore radius r (nm) can be expressed by the following Kelvin equation (2).
ln (P / P ₀ ) = − (2V _m γcos θ) / (rRT) (2)
In the above equation (2), V _m is the molar volume of the adsorbing substance, γ is the surface tension of the adsorbing substance, θ is the contact angle of the adsorbing substance, R is the gas constant, and T is the absolute temperature (K) of the adsorbing substance.

Here, assuming that the adsorbed material is water vapor and the temperature T is 298 K (= 25 ° C.), the molar volume V _m = 18.05 × 10 ⁻⁶ m ³ / mol, the surface tension γ = 72.59 × 10 ⁻³ N / m, and further assuming that the gas constant R = 8.3143 J / deg · mol and the contact angle θ = 0, the above equation (2) becomes the following equation (3).
ln (P / P ₀ ) = − 1.058 / r (3)
From the above equation (3), the relative vapor pressure (P / P ₀ ) is exp for silica having a pore radius r (nm).
It can be seen that at (−1.058 / r), water vapor is condensed into capillaries and rapidly adsorbed in the pores of silica.

Thus, the relative vapor pressure (P / P ₀ ) and the relative humidity at which water vapor is adsorbed by the silica pores are determined mainly by the pore diameter 2r (nm). Therefore, as described above, in silica having a sharp pore size distribution, when the surrounding humidity exceeds a predetermined humidity corresponding to the most frequent pore diameter, moisture absorption is suddenly performed. When the humidity falls below, dehumidification starts abruptly. As a result, silica having a sharp pore size distribution exhibits an excellent humidity control action that allows the ambient humidity to be controlled quickly and accurately to the predetermined humidity.

In addition, the silica of the present invention is such that the total volume of pores having a diameter in the range of D _max ± 20% is 50% or more of the total volume of all pores, and the pores compared with other silicas. By making the distribution sharp, it is possible to control the pore diameter more precisely than in the past. And in this silica, since the pore diameter can be controlled to an arbitrary diameter in the range of 2 to 20 nm, the relative humidity of the surroundings can be arbitrarily set in a wide range of 35 to 90% corresponding to such a pore diameter control. There is an advantage that humidity can be adjusted with high accuracy.

  In addition, producing silica having a pore diameter of 3 to 10 nm and a sharp pore diameter distribution that can be adjusted to a relative humidity of 40% to 60%, which is a comfortable humidity in a living environment, with high reproducibility, Although it was difficult in the conventional silica, the silica of the present invention can control the pores with high accuracy even in the above pore diameter region.

  Now, silica generally tends to deteriorate when heated in the presence of moisture, whereas the silica of the present invention has a very low impurity content and a homogeneous and stable structure with little distortion of the siloxane bond angle. Therefore, even in a harsh environment (for example, high temperature and high humidity), it has characteristics such that there is little change in physical properties such as pore characteristics. Therefore, even if it is used for a long time or repeatedly with a regeneration process by heating, there is an advantage that the pore characteristics and thus the absorption / release characteristics are hardly deteriorated.

And in the silica of this invention, it is manufactured without using an organic template, and there exists an advantage which can manufacture the silica which has said advantage by highly accurate pore control at low cost.
Furthermore, the silica of the present invention is characterized by a relatively high pore volume and a high specific surface area compared to other silicas having the same pore size. The adsorbing material has a higher adsorption capacity and a larger adsorption capacity than other silicas. Therefore, paying attention to the humidity control property, when the moisture absorption capacity of the silica is saturated due to high humidity, the silica will condense, making it impossible to adjust the humidity with the silica. There is an advantage that the humidity can be controlled efficiently with a small amount.

  Further, since the silica of the present invention is amorphous, there is an advantage that it is extremely excellent in productivity.

[2] Binder resin:
The binder resin used in the present invention is arbitrary. However, if the binder resin enters the pores of the silica and fills the pores, the absorption / release performance may be reduced. Therefore, when it is set as the molded object of this invention, it is desirable for binder resin not to fill the silica pore.

  From the above viewpoint, in the present invention, as the binder resin, when the binder resin is in a freely movable state, that is, when the binder resin is in a liquid state or dissolved or dispersed in some solvent ( For example, when the silica and binder resin of the present invention are mixed with a solvent to form a paint, it is desirable to use a material that does not easily enter the pores of silica. Thereby, when manufacturing a resin molding (molding of the present invention), it is possible to prevent the pores of silica from being clogged with the binder resin, and the silica absorption / release performance can be improved.

  As described above, in order to prevent the binder resin from entering the pores of the silica when the binder resin is in a freely movable state, at least one of the following conditions (α) and (β): It is desirable to satisfy either condition.

  Condition (α): A binder resin having a molecular weight of usually 10,000 or more, preferably 20,000 or more, more preferably 30,000 or more, further preferably 35,000 or more, and usually 1,000,000 or less, preferably 800,000 or less, more preferably 500,000 or less is used. By setting the molecular weight of the binder resin to 10,000 or more, it is possible to prevent the binder resin from filling pores of silica (particularly, the silica of the present invention), and by setting the molecular weight to 1,000,000 or less, the silica and binder resin can be prevented. When the paint is used together with the solvent, it can be prevented that the viscosity of the binder resin becomes too high and the handleability of the paint is lowered.

In order to prevent the binder resin from entering the silica pores when the binder resin is in a freely movable state, “molecular weight of the binder resin / moderate diameter of silica (D _max )”. The value of the ratio between the molecular weight of the binder resin and the mode pore diameter (D _max ) of silica represented by the formula (where the unit of the mode pore diameter (D _max ) of silica is “nm”) ) Is usually 200 or more, preferably 2500 or more, more preferably 3000 or more, further preferably 35000 or more, and usually 500000 or less, preferably 100,000 or less, more preferably 50000 or less. This also prevents the binder resin from filling the pores of silica (particularly the silica of the present invention), and when the silica and binder resin are used as a paint together with a solvent, the viscosity of the binder resin becomes too high. It can prevent that the handleability of a coating material falls.

  Condition (β): The binder resin has a glass transition temperature Tg of usually −80 ° C. or higher, preferably −70 ° C. or higher, more preferably −50 ° C. or higher, more preferably −30 ° C. or higher, and usually 110 ° C. or lower. The temperature is preferably 40 ° C. or lower, more preferably 30 ° C. or lower, and further preferably 15 ° C. or lower. This also prevents the binder resin from filling the pores of silica (particularly the silica of the present invention).

  The condition (α) and the condition (β) may satisfy only one or both of them. However, when the organic solvent is used as the solvent, the condition (α) is preferably satisfied when silica and a binder resin are mixed in a solvent as described later, and the condition (β is used when an aqueous solvent is used. ) Is preferably satisfied.

Here, the reason why the binder resin can be prevented from entering the pores of the silica even when the binder resin is in a freely movable state will be described.
As described above, in order to prevent the binder resin from entering into the pores of the silica when the binder resin is in a freely movable state, the diameter of the binder resin is made larger than the diameter of the silica pores. For example, the binder resin may be prevented from entering the silica pores. Here, the diameter of the binder resin refers to the molecular diameter of the binder resin. Particles in which the binder resin is dissolved or dispersed in a solvent such as an organic solvent or an aqueous solvent and the molecules are aggregated (for example, aggregates and colloids). Etc.), the diameter of the binder resin refers to the diameter of the aggregated particles.

  By the way, the diameter (size) of the binder resin is related to the molecular weight of the binder resin, and it is known that the binder resin having a larger molecular weight has a larger diameter. Therefore, when a binder resin that is large enough not to enter the silica pores is selected, a binder resin having a molecular weight in a predetermined range may be selected.

Therefore, a binder resin having a molecular weight within the above range, or a binder resin having a ratio between the molecular weight of the binder resin and the mode pore diameter (D _max ) of silica within the above range is silica (especially of the present invention). (Silica) has a diameter larger than that which makes it difficult to enter the pores of the silica, so that the binder resin can be prevented from entering the silica even when the binder resin is in a freely movable state. Can do. Thereby, it can prevent that binder resin fills the pore of a silica.

The molecular weight of the binder resin can be measured by, for example, GPC (gel permeation chromatograph) or viscosity measurement of a solution in which the binder resin is dissolved.
The diameter D (nm) of the binder resin in the solid state can be usually calculated by the following formula using the density a (g / ml) of the binder resin in the solid state and the molecular weight M of the binder resin. .

Moreover, the diameter of the binder resin when dissolved or dispersed in the solvent is measured from the light scattering intensity obtained by irradiating the solvent with laser light using a multi-angle light scattering detector (MALS) or the like. be able to. Furthermore, a method of measuring the diameter by observing the binder resin with a transmission electron microscope, a method of measuring the diameter from the turbidity of the solvent in which the binder resin is dissolved or dispersed, a CHDF (Capillary Hydrodynamic Fractionation) method, etc. Also, the diameter of the binder resin can be measured.

  Even when the binder resin is dissolved or dispersed in the solvent, if the concentration is high, the polymer chain of the binder resin is in a string shape and has a molecular diameter close to that of the solid state. It is thought that.

However, in the state where the binder resin is not dissolved in the solvent, the polymer chain usually exists in a spherical shape. However, in the dissolved state, the binder resin does not exist as a single molecule but a plurality of molecules are entangled with each other. It may be in a state in which the size has increased or a state in which the molecular size has increased due to swelling. Therefore, even when the diameter of the binder resin calculated from the molecular weight is smaller than the mode pore diameter (D _max ) of silica, the binder resin can be prevented from entering the silica pores in the solvent. There is. As a specific example, in the case of an acrylic resin having an average molecular weight of 95,000, its diameter (molecular size) is 6 nm, but it does not block the silica pores with the most frequent pore diameter (D _max ) of 15 nm. .

Further, the molecular size of the binder resin in a dissolved state also changes depending on the solubility between the binder resin and the solvent. However, in any state, if the ratio of the molecular weight of the binder resin to the mode diameter diameter (D _max ) of silica or the molecular weight of the binder resin is within the above range, the binder resin has no pores of silica. Filling can be prevented.

  In particular, when a binder resin colloids in a solvent (particularly an aqueous solvent) to form an emulsion, the binder resin (colloid) in the emulsion has a structure in which molecules are aggregated, and a surfactant (protective colloid). ) And is large enough not to enter the silica pores. That is, the diameter of the binder resin (here, the diameter of the colloid of the binder resin in the emulsion) is larger than the diameter of the silica pores.

  Even if the molecular weight of the binder resin is not within the above-mentioned range, the size of the colloid of the binder resin is usually large enough not to enter the silica pores regardless of the molecular weight of the binder resin. . Therefore, as long as the colloid of the binder resin is stable, the binder resin can be prevented from entering the silica pores.

  By the way, the stability of the binder resin colloid in the emulsion is related to the glass transition temperature Tg. Therefore, by using a binder resin having a glass transition temperature Tg at which the colloid is stable, it is possible to prevent the binder resin from entering the pores of silica in an emulsion using a solvent. Specifically, if a binder resin having a glass transition temperature Tg of usually −80 ° C. or more and usually 110 ° C. or less is used as described above, the binder resin is silica (in particular, the silica of the present invention) in an emulsion together with a solvent. ) Can be prevented.

  Furthermore, when the glass transition temperature Tg is −80 ° C. or higher, the binder resin can have an appropriate strength. Therefore, a composition of silica and binder resin (for example, the resin composition of the present invention) is molded. In the case of the molded product of the present invention, there is no possibility that the moisture absorption function is deteriorated, the physical properties such as stickiness and handling properties are deteriorated, and silica is easily dispersed. Further, when the glass transition temperature Tg is 110 ° C. or lower, the binder resin is not too hard, and a composition of the silica and the binder resin (for example, the resin composition of the present invention) is molded to form the molded body of the present invention. In this case, it is possible to eliminate the possibility that silica is detached from the molded body, and to improve the texture. The resin composition of the present invention is a composition comprising the silica of the present invention and a binder resin that satisfies at least one of the above conditions (α) and (β), as will be described later. Say. Moreover, the resin composition of this invention is abbreviated as the composition of this invention suitably.

Emulsions are classified into colloidal dispersion (particle diameter: 10 nm to 50 nm), emulsion (50 nm to 500 nm), suspension (0.5 μm to 10 μm) and the like according to the diameter of dispersed particles.
As described above, in the binder resin used for the molded article of the present invention, it is desirable that either the molecular weight or the glass transition temperature Tg satisfies the above conditions. Naturally, both the molecular weight and the glass transition temperature Tg satisfy the above conditions. It is more desirable to satisfy.

  Furthermore, the diameter of the binder resin also increases when the degree of crosslinking of the binder resin is large. Accordingly, a binder resin having a high degree of crosslinking is preferable. Therefore, during the production of the binder resin, the composition of the binder resin and silica such as the composition of the present invention, the crosslink that crosslinks the binder resin to the paint obtained by mixing the binder resin and silica of the present paint and the like in a solvent, etc. It is preferable to mix the agent appropriately. The degree of crosslinking of the binder resin can be measured by examining the solubility in an organic solvent.

  Specific examples of the binder resin include ester cellulose such as nitrocellulose, cellulose acetate and cellulose butylacetate; ether cellulose such as methylcellulose and ethylcellulose; polyamide resin, chlorinated rubber, cyclized rubber, polyvinyl chloride resin, vinyl chloride / Examples thereof include thermoplastic resins such as vinyl acetate copolymer resins, ethylene / vinyl acetate copolymer resins, chlorinated polypropylene, and acrylic resins. Also, alkyd resin, amino alkyd resin, urea resin, melamine resin, melamine / urea resin, phenol resin, resorcinol resin, furan resin, epoxy resin, unsaturated polyester resin, polyurethane resin, polyimide, polyamideimide, polybenzimidazole, poly Examples thereof include thermosetting resins such as benzothiazole.

  In addition, processed oils and fats such as fats and oils, boiled oil, boiled sardine oil, tung oil stand oil, oil-based phenol resin, maleated oil; drying oil-modified phthalic acid resin, non-drying oil-modified phthalic acid resin, modified alkyd resin, epoxy-fatty acid Oils such as ester resins, epoxy-alkyd resins, oil-organized polyurethane resins, or fatty acid-modified phthalic resins; polyester resins such as unsaturated polyester resins, fluorine-modified polyester resins, silicone-modified polyester resins, urethane-modified polyester resins; silicone resins; acrylics Examples include silicone resins; fluorine-containing resins; inorganic resins and the like.

  Furthermore, in addition to resins such as styrene maleic resin, polyvinyl chloride, polyvinyl acetate resin, acrylic resin, polyurethane resin, epoxy ester resin, polyamine resin, natural rubber, recycled rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber Rubber such as chloroprene rubber, butyl rubber, polysulfide rubber, silicone rubber, polyurethane rubber, stereo rubber (synthetic natural rubber), ethylene propylene rubber, block copolymer rubber (SBS, SIS, SEBS, etc.) can also be used as the binder resin. it can.

Furthermore, as will be described later, when the silica and binder resin (for example, the composition of the present invention) is used as a paint together with an aqueous solvent (hydrophilic solvent), the binder resin may be a polyester elastomer, polyurethane, thermal reaction, or the like. It is preferable to use polymers such as type urethane resin, NBR, SBR, acrylic, isocyanate resin, vinyl alcohol resin, polyacrylic acid emulsion, silicone resin, epoxy resin, melamine resin, and polymer latex.
In particular, when the molded article of the present invention is formed by impregnating a base material such as fiber or cloth material with silica and a binder resin (for example, the resin composition of the present invention), flexibility, strength, and weather resistance. From the viewpoints of properties and abrasion resistance, acrylic resins, silicone resins, acrylic polyurethane resins, acrylic silicone resins, and polyurethane resins are preferred, and polycarbonate polyurethanes are particularly preferred. Furthermore, a silicone resin is most preferable from the viewpoint of flexibility and washing durability of a material (a molded body in which silica is fixed to a base material with a binder resin as will be described later).

From the viewpoint of adhesiveness, it is preferable to use a resin contained in the polymer latex as the binder resin. Examples of the polymer latex include synthetic resin latex and rubber latex.
Specific examples of the synthetic resin latex include polyvinyl chloride latex, polyvinylidene chloride latex, polyurethane latex, acrylic resin latex, polyvinyl acetate latex, polyacrylonitrile latex, and modified products and copolymers thereof. Accordingly, examples of the binder resin in this case include polyvinyl chloride, polyvinylidene chloride, polyurethane, acrylic resin, polyvinyl acetate, polyacrylonitrile, and modified products and copolymers thereof.

The acrylic acid latex which is a typical synthetic resin latex will be described in more detail.
A particularly preferable acrylic resin latex is a polymer emulsion mainly composed of (meth) acrylic acid ester. Examples of the (meth) acrylic acid ester as the main component of the binder resin in the polymer emulsion include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, (meth) acrylic acid glycidyl ester, (meth) acrylic acid 2-hydroxyethyl, etc. are mentioned. There are copolymerizable ethylenically unsaturated monomers that are used in combination with this main component, and the monomers include styrene, (meth) acrylonitrile, (meth) acrylic acid amide, N-methylol acrylic. Examples include acid amide, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, (meth) acrylic acid, itaconic acid, fumaric acid, crotonic acid, maleic acid and the like.

  When used in combination with the above monomer, the content of the (meth) acrylic acid ester as the main component is preferably 50% by weight or more. The acrylic resin is preferably formed by an emulsion polymerization method. For example, water, ethylenically unsaturated monomer, emulsifier (sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether, etc.) and radical polymerization initiator are mixed in a nitrogen-substituted reaction vessel, heated and stirred at a predetermined temperature. Polymerize. The particle size of the acrylic resin can be controlled by adjusting the concentration of the emulsifier during the emulsion polymerization.

  Specific examples of the binder resin contained in the rubber latex include natural rubber, styrene butadiene rubber, acrylonitrile rubber, acrylonitrile butadiene rubber, isoprene isobutyl rubber, polyisobutylene, polybutadiene, polyisoprene, polychloroprene, and polyethylene propylene. Is mentioned.

  The butadiene copolymer preferably contains 20 to 80% by weight of butadiene and 20 to 80% by weight of an unsaturated monomer copolymerizable therewith. Unsaturated monomers include methacrylic acid ester, acrylic acid ester, styrene, acrylonitrile, methacrylonitrile, acrylic acid amide, N-methylol acrylic acid amide, vinyl acetate, vinyl chloride, vinylidene chloride, acrylic acid, itaconic acid, fumaric acid , Crotonic acid, maleic acid and the like can be used.

  The copolymer composition of the butadiene copolymer is 20 to 60% by weight of butadiene and 40 to 80% by weight of (meth) acrylic acid ester when heat resistance and weather resistance are required, for example, when used for vehicles. %, And other unsaturated monomers are preferably 0 to 20% by weight.

Furthermore, examples of the binder resin having a glass transition temperature Tg of −80 ° C. to 110 ° C. include acrylic resins, ethylene-vinyl acetate resins, polyurethane resins, butadiene resins, and the like.
Moreover, the said binder resin may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[3] Features of the compact:
The molded article of the present invention is a resin molded article composed of a binder resin and silica, and further, usually 30% or more, preferably 40% or more, more preferably 50% or more of the pore volume of silica. It is characterized by being open to the outside of the molded body, that is, the inside of the pore and the outside of the molded body communicate with each other. The ratio of the volume of pores open to the outside of the molded body of the present invention among the pores of silica is determined by measuring the pore volume for each of the molded body of the present invention, silica, and binder resin. Can be calculated.

In addition, the shape of the molded body of the present invention is arbitrary, for example, a film shape (state when applied to the surface of a base material), a flat plate shape, a sheet shape, a block shape, a pipe shape, a fiber shape (mixed and mixed fibers) It can be formed into a shape such as a case where silica is contained therein.
Further, the molded article of the present invention may be subjected to various treatments as necessary, for example, heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making processing, deep drawing processing, box Processing, tube processing, split processing, etc. can be performed.

  In addition, when the molded body of the present invention is a layered molded body, there is no other limitation as long as it has at least a layer composed of silica and a binder, for example, silica and a binder (for example, the composition of the present invention). A laminated structure composed of a plurality of layers, which may be configured as a single-layer structure composed only of the layers contained, and includes one layer or two or more layers containing silica and a binder (for example, the composition of the present invention). You may comprise as.

  In order to produce a laminated structure, for example, a layer made of another material may be laminated on one side or both sides of a layer containing a silica and binder composition (for example, the composition of the present invention). As a laminating method, for example, a film formed of a composition of silica and a binder resin (for example, the composition of the present invention), a method of melt-extruding other resin on a sheet, and conversely, a substrate made of other resin, A method of melt-extruding a silica and binder composition (for example, the composition of the present invention), a method of co-extruding a silica and binder composition (for example, the composition of the present invention) and another resin, and a silica And a film formed of a binder, a sheet and a film of another substrate, and a method of laminating the sheet using a known adhesive such as an organic titanium compound, an isocyanate compound, or a polyester compound. In addition, the film said to this invention means the film in a broad sense including forms, such as a sheet | seat, a tape, a pipe | tube, a container.

  In addition, for example, the molded body of the present invention can be formed into a honeycomb shape for incorporation into an air conditioner or the like, which can be formed by mixing silica with a binder (binder resin), It is possible to obtain a molded body (resin molded body of the present invention) by using a mixture of a binder resin and water to make a slurry. In some cases, a honeycomb can be produced using only silica. At this time, the slurry containing silica is, for example, silica, usually 2 to 20 parts by weight of organic binder, usually 10 to 50 parts by weight of inorganic binder, and usually 150 to 100 parts by weight of silica. 200 parts by weight of water. As the organic binder, for example, methyl cellulose is used. Moreover, as said inorganic binder, a silica sol etc. are used, for example.

  Furthermore, the molded body of the present invention preferably includes a base material to which the binder resin and the silica are fixed, in addition to molding the silica and the binder resin as they are. That is, it is preferable that the molded body of the present invention is formed by fixing a composition containing silica and a binder resin to a substrate. Thus, the molded body containing a base material can be manufactured by, for example, applying or impregnating a base material with a silica or binder resin dissolved or dispersed in a solvent (for example, the paint of the present invention). it can.

  Here, the substrate is not particularly limited, and any material such as a film, a sheet, a plate material, a fabric made of fiber, paper, plastic, wood, concrete, metal, leather or the like can be used as the substrate. Of these, fibers and sheets are preferred. When fibers are used as the base material, the fibers may be spun into yarn, woven into cloth, or compression molded into fiberboard. Any one of these substrates may be used alone, or two or more thereof may be used in any combination and ratio.

  Examples of the fibers may be natural fibers or synthetic fibers, or fibers using both of them. Further, the fibers may be in any state such as woven fabric, knitted fabric, and non-woven fabric. Specific examples include woven fabric, moquette, towel cloth, tricot, double raschel, circular knitting, needle punch and the like. Examples of the fibers used here include natural fibers such as cotton, hemp, silk, and wool, or rayon; acetate; protein fibers; chlorinated rubber; polyamides such as nylon 6, nylon 66, and nylon-12; Polyvinyl chloride; Polyvinylidene chloride; Polyacrylonitrile; Polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate and polylactic acid; Polyethylene; Polypropylene; Polyurethane; Polycyanide cyanide; Polyfluoroethylene, etc. Examples of the fibers include polymers and blends. From the viewpoint of versatility, it is preferable to use polyester or polyamide. These may also contain other polymers, matting agents, flame retardants, antistatic agents, pigments and other additives.

  Furthermore, you may use the conductive fabric utilized in order to dissipate static electricity effectively. The conductive fabric here is a mixture of conductive substances such as copper, aluminum, stainless steel, carbon, and conductive polymer in the form of particles in the organic fiber, or vacuum deposition method on the surface of the organic fiber. Coated with organic fiber, clad with organic fiber, or conductive fiber made of conductive material itself added to the fabric. The method for adding conductive fibers to the fabric may be any of mixing in the fiber state, mixing in the sliver state, twisting in the form of yarn, mixing or twisting in the form of filament, and arrangement on the structure.

  The single yarn fineness of the fiber is usually 0.01 dtex or more, preferably 0.1 dtex or more, more preferably 1 dtex or more, and usually 100 dtex or less, preferably 10 dtex or less. If it is 100 dtex or less, since there is a sufficient surface area as a fiber, moisture absorption performance can be sufficiently exhibited, which is preferable. Moreover, if it is 0.01 dtex or more, even when it impregnates a silica, since practical mechanical strength as a fiber can be ensured, it is preferable.

  Further, the cross-sectional shape of the synthetic fiber can be freely selected for a round cross-section, a hollow cross-section, a multi-leaf cross-section such as a trilobal cross-section, and other irregular cross-sections. Moreover, there is no restriction | limiting in particular in the form of a synthetic fiber, such as a long fiber and a short fiber. As the fabric, a woven fabric or a knitted fabric can be used depending on the application. A plain woven fabric, a twill weave fabric, a satin weave fabric, a combination thereof, or a knitted fabric may be used.

Furthermore, when the molded body of the present invention is formed by impregnating the base material with a coating material, and the molded body is used as a light diffusion sheet, the shape of the base material is also preferably a sheet shape. In that case, the substrate is preferably formed of a transparent material, and more preferably formed of a colorless and transparent material.
Examples of the transparent material include synthetic resins such as polyethylene terephthalate, polyethylene naphthalate, acrylic resin, polycarbonate, polystyrene, polyolefin, cellulose acetate, and vinyl chloride.
Moreover, although there is no restriction | limiting in particular about the thickness of a transparent raw material, It is desirable to form in the appropriate thickness of 50 micrometers or more and 1 cm or less normally according to the use.

  As described above, when the formed body of the present invention is formed in a honeycomb shape, a honeycomb body made of ceramic or the like can be used as a base material, and silica and binder resin can be applied to the base material. In this case, for example, silica and a binder resin are mixed with a solvent to form a paint, and this is coated on the honeycomb body. As the honeycomb body, for example, cordierite can be used. Silica can be used after filling it into a particle form such as a spherical body or a columnar body. In this case, the size of the particle is usually 0.1 to 30 mm in diameter in a spherical shape, and in a columnar shape in consideration of ensuring the air permeability of the packed portion of the column and ensuring the contact area with water vapor. Usually, it is preferable that the column diameter is 0.1 to 10 mm and the length is about 1 to 30 mm.

  In addition, a column or honeycomb provided with silica is provided with an inlet for introducing air in a space to be conditioned and an outlet for blowing out the conditioned air. Etc.) may be attached. When the column or honeycomb body is attached to an air conditioner or the like, more air can be brought into contact with the silica surface or the humidity adjusting agent by actively passing air in a space to be humidified. Therefore, the humidity of the space can be kept constant in a short time.

Further, when the molded body of the present invention is produced using a base material, silica may be fixed in any state as long as it is fixed to the base material. For example, silica and binder resin are the entire base material. May be fixed to the base material so as to be coated, or may be fixed to be attached to only a part of the base material.
In addition, a base material may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[4] Molded body composition:
The ratio of silica in the molded article of the present invention is arbitrary, but is usually 10% by weight or more, preferably 20% by weight or more, more preferably 40% by weight or more, and usually 95% by weight or less, preferably 90% by weight. Hereinafter, it is more preferable that the content be 80% by weight or less, and more preferably 60% by weight or less. If the silica content is lower than this range, sufficient absorption / release performance may not be exhibited, and if it is higher than this range, the binder resin may not be able to hold the silica.

  Further, the ratio of the binder resin in the molded article of the present invention is also arbitrary, but usually 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, further preferably 40% by weight or more, Usually, it is 90% by weight or less, preferably 80% by weight or less, more preferably 60% by weight or less. If the binder resin content is lower than this range, silica may not be retained, and if it is higher than this range, sufficient absorption / release performance may not be exhibited.

  Further, in the molded article of the present invention, the ratio of silica to binder resin (silica / binder resin) is arbitrary, but is usually 0.1 or more, preferably 0.2 or more, more preferably 0 by weight ratio. 0.5 or more, more preferably 0.6 or more, particularly preferably 0.8 or more, and usually 50 or less, preferably 20 or less, more preferably 10 or less, still more preferably 5 or less, particularly preferably 2 or less. . If the above ratio is smaller than this range, sufficient absorption / release performance may not be exhibited. If the ratio is larger than this range, the binder resin may not be able to hold silica.

  Further, when silica and a binder resin are mixed to form a composition, and the composition is molded into the molded body of the present invention, the composition may be molded as it is. One or both of the resins may be further added and the composition may be adjusted before molding.

  Furthermore, the molded article of the present invention may have other components (additives). Therefore, the molded product of the present invention may contain, in addition to silica and binder resin, a plasticizer, a stabilizer, a surfactant, a crosslinkable substance (crosslinking agent), a filler, and a colorant (coloring material) depending on the usage of the molded product. ), PH adjusters, flame retardants, conductive agents, curing agents, pigment dispersants, emulsifiers, desiccants, antifoaming agents, antiseptics, antifreeze agents, thickeners, heat generation aids, moisture absorption aids, reinforcing materials After blending an appropriate amount of other components such as fiber (glass fiber, carbon fiber, etc., fiber can also be used as a base material), deodorant, antibacterial agent, and functional agent, You can also These other components may be blended at any stage of producing the molded article of the present invention, for example, mixed with the raw material of the molded article of the present invention (that is, silica and binder resin), They may be mixed during the molding process of the molded article of the present invention, or may be introduced after molding. These other components can be mixed not only in the molded article of the present invention but also in the composition and paint of the present invention described later. Alternatively, the molded body of the present invention may be produced after being previously supported in the pores of silica. Furthermore, you may mix by operation, such as an impregnation later, to the resin molding after preparation.

Among these additives, typical ones will be described in detail.
For example, a coloring material may be mixed in order to color the molded article of the present invention. The coloring material may be mixed with a paint (including the paint of the present invention) used in the course of manufacture of the molded article of the present invention, or may be mixed with silica in advance and colored with silica. As the color material, various known color materials can be arbitrarily selected and used. For example, inorganic pigments, organic pigments, dyes, and the like can be used.

  Specific examples of inorganic pigments include natural inorganic pigments such as clay, barium sulfate, calcium carbonate, mica, mica-like iron oxide, ocher, lead white, red lead, yellow lead, silver vermilion, ultramarine, bitumen, cobalt oxide, Synthetic inorganic pigments such as titanium, titanium dioxide coated mica, strontium chromate, titanium yellow, titanium black, carbon black, graphite, zinc chromate, iron black, molybdenum red, molybdenum white, risurge, lithopone, aluminum, gold, silver, copper , Metals such as zinc and iron.

  Specific examples of organic pigments include dye lakes dyed on extender pigments and raked with a precipitant, azo pigments such as soluble azo, insoluble azo, condensed azo, phthalocyanine pigments, nitroso pigments, nitro pigments Examples thereof include pigments, basic dye pigments, acid dye pigments, vat dye pigments, and mordant dye pigments.

Examples of other color materials that can be used include granular, sandy, and powdery materials such as glass, ionomer, AS, ABS, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, polyamide, polyethylene, and polyethylene terephthalate. , Polyvinylidene chloride, polyvinyl chloride, polycarbonate, polyvinyl acetate, polystyrene, polybutadiene, polypropylene, and other thermoplastic resins (plastics), epoxy resins, xylene resins, phenolic resins, unsaturated polyester resins, polyimides, polyurethanes, maleic acid resins And thermosetting resins such as melamine resin and urea resin, which may be colored or non-colored.
In addition, said color material may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Further, for example, a surfactant may be mixed in order to make the paint used in the course of producing the molded article of the present invention into an emulsion. As the surfactant, various known surfactants can be arbitrarily selected and used. For example, tripolyphosphate such as sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, sodium alkylnaphthalenesulfonate, alkylbenzenesulfone, etc. Synthetic polymers such as sodium alkyl acrylate, sodium polyacrylate, polyvinyl alcohol, styrene-maleic acid copolymer, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyoxyethylene phenol ether, poly Polyoxyalkylene aryl ethers such as oxybutylene phenol ether can be used.
In addition, said surfactant may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

Further, for example, a pH adjusting agent may be mixed. By using a pH adjuster, in a paint containing silica and a binder resin, for example, a polymer latex stabilized in an alkaline region (usually pH 8 to 10) such as an acrylic resin latex as a binder resin, and an aqueous solvent The binder resin can be stabilized when, for example, silica having acidity is used. As the pH adjuster, various known pH adjusters can be arbitrarily selected and used, for example, ammonia water or the like.
In addition, a pH adjuster may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Further, for example, a flame retardant may be mixed. As the flame retardant, various known flame retardants can be arbitrarily selected and used, and any of inorganic flame retardants and organic flame retardants can be used. In general, antimony compounds, phosphorus compounds, chlorine compounds, bromine compounds, guanidine compounds, boron compounds, ammonium compounds, brominated diaryl oxides, brominated allenes, and the like are known as flame retardants. Specific examples include antimony trioxide, antimony pentoxide, primary ammonium phosphate, secondary ammonium phosphate, phosphate triester, phosphite, phosphonium salt, phosphate triamide, chlorinated paraffin, dechlorane, Ammonium bromide, tetrabromobisphenol A, tetrabromoethane, guanidine hydrochloride, guanidine carbonate, guanidine phosphate, guanyl urea phosphate, sodium tetraborate decahydrate (borax), ammonium sulfate, ammonium sulfamate, decabromodi Examples include phenyl oxide, hexabromophenyl oxide, bentabromophenyl oxide, hexabromobenzene and the like.
In addition, a flame retardant may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Further, for example, a conductive agent and an antistatic agent may be mixed. As the conductive agent, various known conductive agents can be arbitrarily selected and used. For example, conductive polymers such as conductive carbon black, polyacetylene, and polypyrrole, metal powders such as copper, aluminum, and stainless steel, carbon fibers , Conductive fiber materials such as metal fibers, anionic, cationic, nonionic antistatic agents, quaternary ammonium compounds, and the like can be used.
In addition, a electrically conductive agent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Further, for example, a filler may be mixed. As the filler, known various fillers can be arbitrarily selected and used, for example, hydrous magnesium silicate clay minerals such as sepiolite and palygorskite, activated carbon, activated carbon fiber, silica gel, synthetic zeolite, cristobalite and the like. A porous adsorbing material is mentioned.
In addition, a filler may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

Further, for example, a stabilizer may be mixed for the purpose of improving various durability such as light resistance, heat resistance, water resistance and solvent resistance. As the stabilizer, various known stabilizers can be arbitrarily selected and used. For example, antioxidants, ultraviolet absorbers, hydrolysis inhibitors and the like can be used.
In addition, a stabilizer may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

Further, for example, a crosslinking agent that increases the degree of crosslinking of the binder resin may be mixed for the purpose of improving various durability such as light resistance, heat resistance, water resistance, and solvent resistance. As a crosslinking agent, a well-known crosslinking agent can be arbitrarily selected and used, for example, an epoxy resin, a melamine resin, an isocyanate compound, an aziridine compound, a polycarbodiimide compound, etc. can be used.
In addition, a crosslinking agent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Further, for example, auxiliary agents such as the above-described exothermic auxiliary agent and hygroscopic auxiliary agent may be mixed. These auxiliary agents may be used alone or in combination of two or more in any combination and ratio.

  In addition, water-repellent agents such as silicones and fluorines, hydrophilic agents such as polyethylene glycol, reinforcing fillers, plasticizers, deterioration inhibitors, dispersants, antistatic agents, etc. can also be used. These may be used alone or in combination of two or more in any combination and ratio.

  In addition, the base material may be previously treated with a particle additive. Thereby, a silica and a base material can be firmly fixed. Therefore, for example, when a molded article of the present invention is produced using fibers as a base material and a garment is produced using the produced fibrous molded article, silica can be prevented from being detached from the fiber, and the washing durability of the garment can be prevented. Can be improved. As this particle adhering agent, one that binds two of a base material and silica is used. If a specific example is given, a silane coupling agent etc. will be used suitably. Moreover, you may use these, mixing with a resin composition (for example, composition of this invention) as an additive. In addition, a particle | grain additive may also be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[5] Properties of the molded body:
Since the molded article of the present invention described above uses silica having excellent durability and water resistance, it is high if the kind of binder resin and other components to be used in combination are appropriately selected so as not to impair this property. Durability and water resistance can also be provided.
Furthermore, since the molded product of the present invention has most of the pore volume of silica open to the outside of the molded product, it is possible to sufficiently exhibit the excellent absorption / release performance of silica. In addition, since a large amount of substances can be adsorbed, the molded article of the present invention can exhibit excellent adsorbability (including deodorizing properties due to adsorption of malodorous substances), and excellent adsorbent substances such as drugs. It can exhibit sustained release properties.

Hereinafter, typical examples of the absorption / release performance that can be exhibited by the molded article of the present invention will be described in detail with respect to adsorption exothermic property, humidity control property, hygroscopic exothermic property, drug sustained release property, adsorbability, antibacterial property, and the like. .
<Adsorption exothermic property (hygroscopic exothermic property)>
When any substance is adsorbed on the pores of silica, heat of adsorption is generated. The property of generating heat with this adsorption is adsorption heat generation.
In particular, when the adsorbing substance is moisture, heat is generated due to hydrogen bonding, heat of dissolution, van der Waals force, etc. when porous silica adsorbs water. This property is called hygroscopic exothermic property, and the greater the specific surface area of silica, the greater the amount of heat generated by the chemical bonding force to the silica surface. Moreover, when the pore volume is large, the amount of water adsorbed inside the pores increases, and the heat generation amount can be increased.

  Therefore, in the molded body of the present invention, for example, when an adsorbing substance such as moisture (water) is adsorbed, heat of adsorption is generated. At this time, since the molded body of the present invention can adsorb a large amount of substance (in this example, water) as described above, a large heat of adsorption is generated. In other words, this means that the molded article of the present invention has excellent adsorption heat generation and moisture absorption heat generation.

Therefore, the molded article of the present invention has the following advantages, for example. When a molded product of the present invention is formed using some fiber as a base material and a garment is manufactured using the molded product (ie, fiber), the garment quickly absorbs moisture such as sweat immediately after wearing and generates heat. Therefore, it is possible to reduce the feeling of cold immediately after clothing.
In addition, as described above, when the exothermic aid is used in the molded article of the present invention, the adsorption exothermic property and the hygroscopic exothermic property are further increased, and heat can be generated more effectively.
Further, when the pore size distribution of silica is sharp, the adsorption rate is increased, so that the heat generation rate is also increased. Therefore, when the silica of the present invention having a sharp pore size distribution is used as the silica, the heat generation performance is further improved.

<Hygroscopicity>
Silica is a porous material and has the property of adsorbing and desorbing water vapor with a specific water vapor pressure depending on the pore diameter. Therefore, by controlling the pore diameter of silica, adsorption and desorption behavior of water vapor (humidity) can be controlled, and humidity control can be performed. Therefore, humidity control is possible by using the molded article of the present invention that can exhibit such properties of silica. As a specific example, when a garment is manufactured with fibers using the molded article of the present invention as described above, the inside of the garment can be kept at a predetermined humidity (ie, humidity adjustment). In addition, the sharper the pore distribution of the silica used (that is, the more the pore diameters are equal), the higher the moisture absorption / release response to subtle changes in environmental humidity, and the higher the ability to adjust the humidity to a constant humidity. Therefore, when the silica of the present invention is used as silica, the humidity control performance is further improved. Furthermore, when the silica of this invention has a moisture absorption adjuvant, the molded object using the silica is excellent in humidity control property especially.

<Slow drug release>
One of the functions of silica is sustained release. By utilizing this, the molded article of the present invention can be provided with sustained release properties. In particular, when attention is paid to sustained drug release, it is considered that the applicability of the molded article of the present invention increases. For example, there is a method in which clothes are provided with sustained drug release properties in order to improve the functionality of clothes. As a specific example, when a garment is manufactured with the fiber using the molded article of the present invention as described above, the drug that exhibits moisture retention, vitamin supplementation, whitening, healing effect, etc. on the silica of the molded article of the present invention constituting the garment Can be supported. Thereby, the sustained release effect of a fragrance | flavor, a skin care component, etc. increases, and it comes to be able to exhibit a high skin care effect. Moreover, compared with the conventional product which carried these chemical | medical agents on the conventional clothes, there exists an effect which improves washing durability. Examples of the drug to be supported include vitamin C (such as ascorbic acid derivative), vitamin E, collagen, sericin, chitosan, hipa oil (hinokitiol), squalane, aloe extract, protein, and the like.

In addition, it is preferable from the viewpoint of stability that a surfactant is used together with the drug. Any surfactant can be used. For example, anionic, cationic, and nonionic surfactants can be used. Specific examples include various fatty acid soaps, sodium lauryl sulfate, higher alcohol sodium sulfate, sodium dodecylbenzenesulfonate, sodium dialkylphosphosuccinate, potassium alkyl phosphate, sodium polyoxyethylene alkyl ether sulfate, and the like. Moreover, you may use these with a nonionic surfactant suitably. Nonionic surfactants are also optional, and for example, polyoxyethylene derivatives, sorbitan monoalkylates, sorbitan dialchelates, sorbitan trialchelates, and the like can be used.
Further, from the viewpoint of washing durability, it is preferable to fix the surfactant to a part of silica. In this case, it is preferable to introduce the drug after producing the molded article of the present invention because mixing of the resin and the drug is avoided.

<Adsorption>
The basic gas can be adsorbed on the silica surface of the molded body by ionic bonds by the hydroxyl group present on the silica surface. For example, ammonia, pyridine, trimethylamine, indole and the like can be adsorbed. These substances are causative substances of bad odors such as sweat odor, aging odor, excretion odor, tobacco odor, and garbage odor, but by using the molded article of the present invention, deodorization and removal can be performed using silica. For example, when a garment is manufactured with fibers using the molded article of the present invention as described above, the environment in the garment can be kept clean.

<Antimicrobial properties>
By preliminarily supporting the deodorant and antibacterial substance on the silica of the molded product of the present invention, the molded product of the present invention can be provided with a deodorant and antibacterial effect. Antibacterial substances include organic antibacterial agents such as phenolic, carboxylate, piguanide, halogen, and surfactants, inorganic antibacterial agents such as silver, and naturally derived antibacterial agents such as chitosan and catechin. .

  Further, in order to provide the molded article of the present invention with a deodorizing effect, various metals are supported on silica, or silica is changed to 3-mercaptopropyl group-modified silica to adsorb and eliminate methyl mercaptan, hydrogen sulfide, and the like. It can also smell. Furthermore, nonal, acetaldehyde, etc. can be deodorized by using silica as a 3-aminopropyl group-modified silica. In this way, modifying the end group of silica is also an effective means for providing the molded article of the present invention with a function.

<Other effects>
In addition to the various effects described above, according to the molded body of the present invention, various effects can be obtained. Here, as one specific example, an effect associated with the adsorption of a functional component during washing will be described.

  A detergent used for washing when a molded product of the present invention is produced using a fiber as a base material, and a textile product such as a cloth material or clothes is manufactured using the molded product (ie, fiber). Various functional components contained in the softener / finishing agent, for example, aroma components, deodorant components, masking components, softener components, adsorbing components, antibacterial components, and the like are adsorbed to the silica pores. Thus, the functional component adsorbed in the pores of the silica remains in a large amount in the fiber product even after the washing is completed, and further, the functional component exerts the function that these functional components exhibit by being gradually released from the silica. Various effects will be seen, such as being strengthened and the function lasting longer.

  In particular, when a softener component is used at the time of washing, a more characteristic effect is seen. The softener component usually comprises a surfactant whose hydrophilic group is positively charged. As described above, hydroxyl groups remain on the surface of the pores of the silica, and thus are negatively charged. Therefore, the softener component having a positively charged hydrophilic group is well adsorbed (the detergent component is also a surfactant). However, since the hydrophilic group is usually negatively charged, it is difficult to be adsorbed in the pores of silica.) As described above, when the softening agent component is adsorbed to the pores of the silica during washing, the softening agent component itself has a function of preventing static electricity and suppressing entanglement and is maintained for a long time. When the silica of the present invention described above is used as silica, since the pore volume and specific surface area are larger than those of conventional silica, more softener components are adsorbed and the obtained effect is more remarkable. It becomes.

  Further, when the softener component is adsorbed to the pores of silica, the hydrophobic group of the softener component is immobilized on the inner surface of the silica pores. These hydrophobic groups include these functional components in the pores when other functional components (fragrance component, deodorant component, masking component, adsorption component, antibacterial component, etc.) enter the pores of silica. Has the effect of As a result, the amount of adsorption of these functional components by the silica pores increases, and the adsorption holding power and sustained release performance also improve. Therefore, the effects of the functional component (aroma effect, deodorization effect, masking effect, adsorption effect, antibacterial effect, etc.) are further strengthened, and the effect is stably exhibited over a long period of time.

[II] Method for producing resin molded body:
There is no restriction | limiting in particular about the manufacturing method of the molded object of this invention, If it is a method which can manufacture the above-mentioned molded object of this invention, it can manufacture by arbitrary manufacturing methods. However, it is usually desirable to produce the composition of the present invention described later by molding.
In particular, it is preferable to perform molding by mixing a binder resin, silica, and a solvent, and then removing the mixed solvent. There is no restriction | limiting in the solvent used in this case, Although arbitrary solvents can be used, Usually, it is preferable to use an organic solvent or an aqueous solvent.

  Hereinafter, in the description of the method for producing a molded article of the present invention, a mixture of a binder resin and silica in a solvent is referred to as a paint. In particular, among the paints referred to herein, a mixture of a binder resin that satisfies at least one of the above conditions (α) and (β), the silica of the present invention, and a solvent is a composition of the present invention in a solvent. It corresponds to the coating material of this invention. Accordingly, when the molded article of the present invention is produced from the composition of the present invention, it can also be produced by removing the solvent from the paint of the present invention. The paint may contain the silica and binder resin of the present invention in the solvent in any state such as a solution, a dispersion, or an emulsion.

  Hereinafter, the method for producing the molded article of the present invention by mixing the binder resin, silica and solvent and then removing the mixed solvent (hereinafter referred to as “the production method of the present invention” as appropriate) will be described. To do.

[1] Mixing of silica, binder resin, and solvent:
In the production method of the present invention, first, silica and a binder resin are mixed in a solvent. Thereby, a coating material will be manufactured.
The solvent used in the production method of the present invention is not particularly limited as long as it can dissolve or disperse the above-described binder resin and silica.

  However, when the binder resin satisfies the condition (α), that is, when the molecular weight of the binder resin is in the range of 10,000 to 1,000,000, an organic solvent is preferably used as the solvent. In this case, the coating material to be produced by mixing the binder resin, silica and organic solvent contains the binder resin and silica composition (for example, the composition of the present invention) in the organic solvent. Thus, a liquid in an arbitrary state such as a solution, a dispersion, or an emulsion is obtained.

  When the binder resin satisfies the condition (β), that is, when the glass transition temperature Tg of the binder resin is in the range of −80 ° C. or higher and 110 ° C. or lower, it is preferable to use an aqueous solvent as the solvent. . In this case, the coating material to be produced by mixing the binder resin, silica and solvent contains the binder resin and silica composition (for example, the composition of the present invention) in an aqueous solvent. , Liquids in any state, such as solutions, dispersions, and emulsions. In addition, when using what has already become aqueous emulsion in aqueous solvent as binder resin, a coating material can be manufactured, without further mixing an aqueous solvent when making it mix with a silica.

When the binder resin satisfies both the condition (α) and the condition (β), the solvent to be used can be preferably used, whether it is an organic solvent or an aqueous solvent.
Further, the solvent is preferably a solvent that can be easily removed by drying, heating or the like, both of the organic solvent and the aqueous solvent. Moreover, when performing application | coating or impregnation to a base material, what does not impair the base material which is the object of application | coating or impregnation is preferable.

  Hereinafter, each of the organic solvent and the aqueous solvent will be described. In the following description, when the organic solvent and the aqueous solvent are described without distinction, they are simply referred to as “solvent”.

[1-1] Organic solvent:
There is no restriction | limiting in particular about an organic solvent, A well-known organic solvent can be used arbitrarily. As described above, if the value of the ratio between the molecular weight of the binder resin and the mode pore diameter (D _max ) of the silica is within the predetermined range, the binder resin will not enter the silica pores. The molded article of the invention can be produced stably.

  Among organic solvents, especially those that do not easily enter the silica pores (for example, those that have a large contact angle with silica) may cause the binder resin to enter the silica pores in the paint. Can be prevented, which is preferable.

  Moreover, it is also preferable to use a poor solvent with respect to binder resin as an organic solvent, or to add a partly poor solvent in a solvent. Accordingly, the polymer chain of the binder resin can be dissolved in the organic solvent without being completely stretched (that is, kept entangled), and the binder resin can be prevented from entering the silica pores.

  Furthermore, it is also preferable to use an organic solvent having a high viscosity from the viewpoint of not extending the polymer chain of the binder resin. However, in consideration of the usage, the operation may be difficult when coating, for example.

Specific examples of organic solvents that can be used include chain hydrocarbons such as neopentane, n-hexane, n-heptane, and solvesso, aromatic hydrocarbons such as toluene and xylene, and halogenated carbons such as trichloroethylene and perchloroethylene. Alcohols such as hydrogen, methanol, ethanol, isopropanol and n-butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and n-butyl acetate, ethers such as cellosolve, butylsolve and cellosolve acetate And mineral spirit (hydrocarbon oil).
In addition, the said organic solvent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[1-2] Aqueous solvent:
There is no restriction | limiting in particular about an aqueous solvent, A well-known aqueous solvent can be used arbitrarily. As described above, when the glass transition temperature Tg of the binder resin is within the predetermined range, the binder resin does not form a colloid and does not enter the pores of the silica. can do. That is, when an aqueous emulsion is used, since the binder resin diameter (resin size) in a dispersed state can be expected to be considerably larger than the pore diameter of silica as described above, the binder resin is contained in the silica pores. Intrusion can be prevented.

Further, the aqueous solvent has an advantage that the equipment does not need to be explosion-proof.
In addition, there is an advantage that the use and generation of substances that are undesirable in the environment can be suppressed. This is because it is preferable not to generate an organic solvent as much as possible when complete sealing is difficult.
Furthermore, when an aqueous solvent is used, when the molded product of the present invention is molded as described later, the amount of the remaining organic solvent can be easily reduced from the molded product, and the adhesive force can be improved.

  By the way, when the binder resin is made to exist as an aqueous emulsion using an aqueous solvent, the temperature at which the solidification characteristics are manifested is an appropriate temperature depending on the type, application, usage environment, etc. of the substrate to which the paint is applied. It is desirable to use an aqueous emulsion. Thereby, even when the base material to which the paint is applied is not excellent in heat resistance, the paint can be applied. The temperature at which the coagulation characteristics of the aqueous emulsion are manifested is the temperature at which the emulsion loses its fluidity and solidifies when the emulsion containing various additives is heated with stirring, such as an additive that lowers the dew point. It is possible to adjust the coagulation temperature by adding.

In addition, when a water-based solvent is used as the solvent and the paint is made into a water-based emulsion, if silica is dispersed in water-based solvent in advance of the binder resin, the pores of silica are filled with water and stable. In addition, since the binder resin to be mixed later is also stabilized outside the pores, when the materials to be stabilized are mixed with each other, the binder resin must be broken into individual polymer chains and enter the pores of silica. It is thought that there is no.
Specific examples of the aqueous solvent that can be used include water and an arbitrary aqueous solution. Moreover, you may use the liquid mixture which mixed water and aqueous solution, and the organic solvent suitably.

[1-3] Ratio of silica, binder resin and solvent:
When mixing the silica, the binder resin and the solvent, the ratio of silica in the paint produced by mixing is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, and usually 50%. % By weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, and further preferably 25% by weight or less. If the silica content is lower than this range, the paint may not exhibit sufficient absorption / release performance after application, and if it exceeds this range, the applicability of the paint may decrease.

  In particular, when fibers are used as the base material, the proportion of silica in the paint (attaching coating solution) is usually 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.2% by weight. In addition, it is desirable that the amount is usually 50% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less. Furthermore, as will be described later, when the molded article of the present invention is produced by impregnating the paint into the fiber, the concentration of the functional particles (for example, silica and additives) in the paint and the squeeze rate are optimized. The amount of functional particles applied to the substrate is determined.

  The ratio of the binder resin in the coating is usually 0.5% by weight or more, preferably 1% by weight or more, more preferably 1.5% by weight or more, still more preferably 2.5% by weight or more, particularly preferably. 3 wt% or more, preferably 5 wt% or more, and usually 40 wt% or less, preferably 30 wt% or less, more preferably 25 wt% or less. If the content of the binder resin is smaller than this range, the adhesion of the paint may be lowered. If the content is larger than this range, the absorption / release performance of the molded article of the present invention obtained after application of the paint is lowered. It is because there is a possibility of doing.

  When fibers are used as the base material, the ratio of the binder resin in the paint (attaching coating solution) is usually 0.01% by weight or more, preferably 0.02% by weight or more, more preferably 0.05% by weight. % Or more, usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less. If the ratio of the binder resin is smaller than this range, functional particles (for example, silica and additives) may not be retained, and if the ratio is larger than this range, the desired function will be sufficiently exhibited. There is a possibility of not being able to.

  Further, the ratio of the solvent in the coating is usually 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and usually 98% by weight or less, preferably 90% by weight or less, more preferably 80%. % By weight or less, more preferably 70% by weight or less. If the solvent content is lower than this range, the coating property of the paint may be lowered. If the solvent content is higher than this range, the amount of silica or binder resin contained in the paint will be too small, and drying may be caused. This is because it takes a long time and the workability may be deteriorated.

  In particular, when fibers are used as the substrate, the ratio of the solvent in the paint is usually 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and usually 99.95% by weight or less. Preferably it is 99.90 weight% or less, More preferably, it is 99.75 weight% or less, More preferably, it is 99.5 weight% or less.

  Further, the ratio of silica to binder resin (silica / binder resin) in the paint is usually 0.1 or more, preferably 0.2 or more, more preferably 0.5 or more, and still more preferably 0 by weight. .6 or more, particularly preferably 0.8 or more, and usually 50 or less, preferably 20 or less, more preferably 10 or less. If the ratio is smaller than this range, sufficient absorption / release performance may not be exhibited. If the ratio is larger than this range, the binder resin cannot fully hold the silica when the paint is dried. There is a fear.

[1-4] Other components in paint:
In addition to silica and a binder resin and a solvent, the coating material may appropriately contain another substance (additive). The components that may be contained in these paints are the same as those that may be contained in the molded article of the present invention (that is, for example, auxiliary agents, useful foreign elements, useful organic groups, additives). Etc.). Furthermore, the component that the paint may contain may be added to the paint at any stage before, during, or after the mixing of the silica, the binder resin, and the solvent.
Usually, it is preferable that the molecular weight of these additives is large. This is to prevent the additive from entering the pores of silica. However, when the additive is supported on silica to provide a function, when the additive is introduced into the material later, it is necessary to put it in the pores, so that the molecular weight is preferably small.

[2] Removal of solvent:
After molding a mixture of a binder resin, silica, and a solvent, the molded product of the present invention is produced by removing the solvent. That is, the molded article of the present invention is produced by removing the solvent after molding the paint. The molding method and the solvent removal method are arbitrary.
As a specific example, a coating is applied to a base material to be applied to form a coating film of the coating, and then the solvent is dried and removed from the coating film to form the molded body of the present invention, or Examples of the method include impregnating a base material with a paint and separately forming a paint layer and then removing the solvent from the layer to form the formed article of the present invention.

[2-1] Application:
When molding is performed by coating, a coating is applied to the substrate to form a coating film, and the solvent is removed from the coating film to solidify the binder resin, thereby obtaining the molded body of the present invention.
There is no restriction | limiting in particular about the base material used as the application object of a coating material, As mentioned above, a coating material can be apply | coated using arbitrary things as a base material. Specific examples of the base material include films, sheets, plate materials, fibers, fabrics, leathers and the like made of paper, plastic, wood, concrete, metal and the like.

  Specific methods include, for example, a method in which a coating material is applied to a substrate to be coated, a solvent is removed by drying, and the molded article of the present invention is formed as a coating film (coating layer) on the surface of the substrate. . The formed coating film is a molded article of the present invention containing silica and a binder resin, and has high absorption / release performance. Therefore, the substrate on which the coating film is formed can acquire high absorption / release performance. .

  Here, there is no restriction | limiting in particular about the application | coating method, The method used normally can be used arbitrarily. Specific examples include brushing, spraying, electrostatic coating, roll coating, dip coating, bar coating, floating knife coater, knife over roll coater, reverse roll coater, roll doctor coater, gravure roll coater, air Examples include knife coaters, curtain coaters, kiss roll coaters, nip roll coaters, cast coaters, contour direct coaters, contour reverse coaters, slit coaters, laminates, bonding methods, pad methods, blade coating methods, and ink jet methods. These methods are preferably used in various ways depending on the viscosity and amount of the paint, the characteristics of the paint, the characteristics of the substrate to be applied, and the like. Further, these coating methods may be appropriately combined.

  Moreover, there is no restriction | limiting in particular also about the method of drying the coating material of this invention after application | coating, and removing a solvent, Arbitrary methods can be used. For example, a method such as natural drying, heat drying, vacuum drying, baking, ultraviolet irradiation, electron beam irradiation, or the like may be used as appropriate according to the properties of the paint of the present invention. These drying methods may be combined appropriately.

[2-2] Impregnation:
In the case of molding by impregnation, an impregnated base material (hereinafter referred to as “impregnating member” as appropriate) is impregnated with a paint, and the solvent is removed to solidify the binder resin to obtain the molded article of the present invention.

  The impregnating member to be impregnated with the paint is arbitrary, and the material and shape thereof can be arbitrarily selected according to the application. Specific examples thereof include fibers such as felt, non-woven fabric, and cloth materials made of natural fibers, synthetic fibers, rock wool, glass fibers, carbon fibers, etc., paper, ceramic sheets, leather, waterproof / breathable sheets, etc. A sheet etc. are mentioned. In addition, the impregnating member here includes not only impregnating all but impregnating a part when impregnating the paint. For example, when impregnation is performed from one side of the thickness of the impregnating member, the other side is not impregnated, thereby causing a difference in properties (e.g., adhesion) between the one side of the impregnating member and the other side. This difference may be used (such as bonding the other side).

  Particularly, examples of the impregnating member suitable for impregnating the paint include fibers. Specific examples thereof include the same fibers as exemplified in the description of the configuration of the molded body.

  There is no particular limitation on the impregnation method, and the impregnation may be performed by any method. For example, a method of immersing the impregnating member in a tank filled with paint (so-called dipping) or a method of applying from one or both sides of the impregnating member by a known application means can be mentioned. After the paint has sufficiently penetrated, the surplus is scraped or removed with an appropriate scraping device or removal device such as a suction doctor, doctor roll, or wire bar with a wire wrapped around a round bar. The impregnating member is impregnated with an amount of silica and binder resin. These impregnation methods may be combined as appropriate.

After impregnation, the impregnating member is dried to remove the solvent, and the molded article of the present invention can be obtained.
There is no restriction | limiting in particular also about the method of drying the coating material of this invention, Arbitrary methods can be used similarly to the case of application | coating.

[2-3] Others:
Moreover, when forming a coating film on a base material using a coating material etc., it can also implement in combination with another coating film or layer. As a specific example, it can be combined with a primer layer or a makeup coat.

  The primer layer is a layer formed between the base material and the coating film of the paint, and is a layer made of an appropriate material according to the type of the base material and the properties of the silica and the binder resin. By forming a primer layer, for example, the adhesion of the paint film to the base material is improved to improve the durability of the product, or the surface of the base material is improved to make the paint film uniform. It is effective to form. Moreover, when a base material consists of metals, the effect of rust prevention can also be acquired by forming a suitable primer layer.

  A decorative coat is a layer that is usually formed on the outside of a paint film, and is a layer that is formed to improve the design (designability) of the substrate. As a method of applying makeup, there are methods such as coloring, printing, embossing, and wiping coating. These makeup methods can be applied by combining two or more appropriately. Moreover, you may form a transparent resin protective layer in the outermost surface which gave makeup by application | coating of a transparent resin coating, or the lamination of a transparent resin sheet. However, when the paint includes a color material, it is possible to improve the design by using the paint itself for drawing or the like instead of using the cosmetic coat.

  In addition, these primer layers, decorative coats, transparent resin protective layers, etc. are formed directly on the layer of the molded article of the present invention such as a base material or a coating film, and other members such as appropriate paper and plastic sheets. It is also possible to install a substrate prepared as a separate sheet from the base material or the layer of the molded body of the present invention such as a coating film. Furthermore, an adhesive layer or a pressure-sensitive adhesive layer may be provided between the layer of the molded article of the present invention, such as a base material, a primer layer, and a coating film, a decorative coat, a transparent resin protective layer, and the like.

  As described above, since the above-mentioned paint contains silica and binder resin, which are components of the molded article of the present invention, the coating film obtained by applying it also comprises silica and binder resin. A layer (eg containing the composition of the invention) is formed. Therefore, the coating film formed by applying the paint or the molded body formed by impregnating the paint into the impregnating member exhibits high adsorption performance and is excellent in moisture absorption heat generation and sustained release, durability, Excellent weather resistance. In addition, when the molded body of the present invention is produced by applying a paint to a base material, the molded body has a structure in which the base material to be applied is covered with silica having a large pore volume. Excellent physical properties such as waterproofness and soundproofing. In addition, it is also possible to use the said coating material for purposes other than manufacture of the molded object of this invention.

  Of course, you may manufacture the molded object of this invention by methods other than the manufacturing method of this invention, without using the said coating material. For example, the molded article of the present invention may be produced by mixing silica, a binder resin, additives and auxiliaries that are used as appropriate, and kneading and molding. Moreover, when manufacturing a molded object by methods other than the manufacturing method of this invention in this way, press molding, extrusion molding (T-die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion, etc.), The molded body of the present invention may be manufactured by performing injection molding or the like. Further, for example, two-color molding, injection blow molding, or the like may be performed, and thereby, a molded product with good dimensional accuracy can be obtained.

[III] Resin composition of the present invention:
[1] Composition of composition:
The resin composition of the present invention (the composition of the present invention) is a resin composition comprising at least silica and a binder resin. However, the silica used in the composition of the present invention contains at least the silica of the present invention described above. Further, the binder resin satisfies at least one of the condition (α) and the condition (β). The binder resin more preferably satisfies both the above condition (α) and condition (β).

  In the composition of the present invention as well, the binder resin is prevented from entering the pores in the silica as in the molded product of the present invention. For this reason, normally, the pores of silica are not filled with the binder resin, and various advantages such as the absorption / release performance of the silica of the present invention can be effectively utilized. Further, the composition of the present invention is suitable for use as a raw material for the molded article of the present invention, and can be formed into the molded article of the present invention by molding.

Since the silica used in the composition of the present invention has already been described as the silica of the present invention, the description thereof is omitted here. However, the composition of the present invention may contain silica other than the silica of the present invention.
The binder resin used in the composition of the present invention is not limited as long as it is a binder resin that satisfies at least one of the conditions (α) and (β). The molecular weight, glass transition temperature Tg, degree of crosslinking, specific examples, and the like are also the same as those described above as the binder resin in the description of the molded article of the present invention. However, the composition of the present invention may contain a binder resin that does not satisfy any of the conditions (α) and (β).

  In addition to the silica and binder resin, the composition of the present invention contains various known substances (additives, auxiliaries, useful foreign elements, useful organic groups, etc.) in addition to silica and binder resin. A function can be imparted to form a composite functional composition. Specifically, chemical resistance, deodorant properties, abrasion resistance, weather resistance, antibacterial properties, flame resistance, flame resistance, heat retention, heat insulation, UV-cutting properties, aromaticity, light diffusibility, conductivity And the case of imparting stability and the like. Specific examples of other components that can be contained as additives and auxiliaries include the same components as those described above in the description of the molded article of the present invention.

[2] Composition of composition:
The composition of the composition of the present invention is the same as that of the molded article of the present invention.
That is, although the composition of the present invention varies depending on the use, the silica of the present invention is usually 10% by weight or more, preferably 20% by weight or more, more preferably 40% by weight or more, and usually 95% by weight or less. The content is preferably 90% by weight or less, more preferably 80% by weight or less, and still more preferably 60% by weight or less. If the silica content of the present invention is less than this range, the silica absorption / release performance may not be fully exhibited, and if it is greater than this range, the binder resin may not hold the silica of the present invention. There is a risk of disappearing.

  In the composition of the present invention, the binder resin satisfying at least one of the condition (α) and the condition (β) is usually 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more. The content is preferably 40% by weight or more, and usually 90% by weight or less, preferably 80% by weight or less, more preferably 60% by weight or less. If the content of the binder resin is smaller than this range, the silica of the present invention may not be retained, and if it is larger than this range, the silica absorption / release performance may not be sufficiently exhibited.

  Furthermore, in the composition of the present invention, the ratio of the silica of the present invention to the binder resin satisfying at least one of the conditions (α) and (β) (silica / binder resin) is usually 0 by weight. 0.1 or more, preferably 0.2 or more, more preferably 0.5 or more, still more preferably 0.6 or more, particularly preferably 0.8 or more, and usually 50 or less, preferably 20 or less, more preferably 10 Hereinafter, it is more preferably 5 or less, particularly preferably 2 or less. If the above ratio is smaller than this range, the silica absorption / release performance may not be sufficiently exhibited. If the ratio is larger than this range, the binder resin may not be able to hold the silica of the present invention. .

[3] Characteristics of the composition:
In the composition of the present invention, the binder resin can be prevented from entering into the pores of the silica of the present invention. It can exhibit excellent properties such as adsorption exothermic property, humidity control property, moisture absorption exothermic property, drug sustained release property, adsorptive property, and antibacterial property.
Further, in the composition of the present invention, since the silica pore diameter distribution has a sharp and uniform structure, the silica has a uniform strength, and therefore the composition of the present invention is stable and high. Durability and weather resistance can be achieved.

[4] Use of composition:
The use of the composition of the present invention is arbitrary, but it is preferable to form it and use it as the molded article of the present invention. In addition, it can be used as a paint as a liquid together with a solvent.

  As described above, the composition of the present invention can be used as the molded article of the present invention by molding into an arbitrary shape. The molding method is arbitrary, but as described in the explanation of the molded body of the present invention, if the molding is performed by applying or impregnating the coating material to the base material, the excellent characteristics of silica can be exhibited effectively. Is preferable. That is, it is preferable to form a molded body by mixing the composition of the present invention and a solvent and then removing the mixed solvent. At the time of molding, a mixture of the silica of the present invention, a binder resin satisfying at least one of the conditions (α) and (β), and a solvent contains the composition of the present invention in the solvent. This is the paint of the present invention described later.

[IV] Paint of the present invention:
[1] Composition and composition of paint:
The paint of the present invention contains the above-described composition of the present invention in a solvent, that is, at least silica of the present invention and a binder resin satisfying at least one of the conditions (α) and (β). Is contained in a solvent. Moreover, although the manufacturing method is arbitrary, it can manufacture normally like the coating material demonstrated in the manufacturing method of the molded object of this invention.

  Also in the coating material of the present invention, in the same manner as the coating material described in the method for producing a molded body of the present invention, since the penetration of the binder resin into the pores of silica is suppressed, when applied to some substrate and dried Furthermore, the molded article of the present invention can be easily produced as a coating film.

  Regarding the components of the composition of the present invention contained in the paint, that is, the silica of the present invention, the binder resin, and other components (additives, auxiliaries, useful foreign elements, useful organic groups, etc.) used as appropriate, Since it was mentioned above in description of the molded object and composition of this invention, the description is abbreviate | omitted here.

  Moreover, the solvent used for the coating material of the present invention is the same as the coating material described in the method for producing a molded body of the present invention. That is, when the binder resin satisfies the condition (α), it is preferable to use an organic solvent as the solvent. When the binder resin satisfies the condition (β), it is preferable to use an aqueous solvent as the solvent. The point, the nature of the solvent, specific examples, the amount used, the removal method, and the like are the same as those of the paint described in the method for producing a molded article of the present invention.

[2] Paint characteristics:
Since the paint of the present invention contains silica and binder resin, which are the components of the composition of the present invention, the coating film obtained by applying it to the base material and the base material (impregnating member) are impregnated. The formed molded body becomes the molded body of the present invention, and forms a layer made of silica and a binder resin. Therefore, a coating formed by applying a paint or a molded product formed by impregnating an impregnating member with a paint exhibits high adsorption performance as well as that described in the molded product of the present invention, and the adsorption possessed by silica. Excellent properties such as exothermic property, humidity control property, hygroscopic exothermic property, sustained drug release property, adsorptivity and antibacterial property can be exhibited. Further, at the time of application, the molded body formed by the coating film has a structure in which the object to be applied is covered with silica having a large pore volume, and thus exhibits excellent physical properties such as waterproofness and soundproofing. Further, since the silica pore diameter distribution has a sharp and uniform structure, the silica has a uniform strength, and thus a molded body such as a coating film formed from the paint of the present invention is stable. High durability and weather resistance can also be achieved.

The base material to which the paint of the present invention is applied and the application methods such as coating and impregnation are the same as those described in the method for producing a molded body of the present invention.
In addition, when applied to or impregnated into the base material, it can be carried out in combination with other coatings or layers (primer layer, cosmetic coat, etc.), as with the paint described in the method for producing a molded article of the present invention. It is.

[3] Use of paint:
Although the use of the coating material of this invention is arbitrary, it is preferable to shape | mold and use as a molded object of this invention.

[V] Uses of molded body, composition and paint:
As described above, the molded article, composition, and paint of the present invention have high absorption / release performance and are excellent in moisture absorption exothermic property and sustained release property. In addition, the silica used in the present invention (particularly the silica of the present invention) has excellent properties such as humidity control, sustained release and low refractive index in addition to absorption / release performance and moisture absorption exothermicity. The body, the composition, and the paint effectively exhibit the properties of the silica used in the present invention.

From the above, the molded article, composition and paint of the present invention can be widely used in the following fields, for example.
For example, in application fields used for manufacturing and processing products in industrial facilities, various catalysts and catalyst carriers (acid-base catalysts, photocatalysts, noble metal catalysts, etc.), wastewater / waste oil treatment agents, odor treatment agents, gas separation agents, Applications include industrial desiccants, bioreactors, bioseparators, membrane reactors and the like.

In addition, for example, in building materials, there are applications such as humidity control materials, soundproofing / sound absorbing materials, refractories, and heat insulating materials.
Further, for example, in applications in the air conditioning field, desiccant air conditioners, heat pump heat storage agents, and the like.
Also, for example, in the field of paint / ink applications, there are uses such as matting agents, viscosity modifiers, chromaticity modifiers, anti-settling agents, antifoaming agents, ink back-through preventing agents, stamping foils, and wallpapering. .

  Also, for example, in the field of resin additives, anti-blocking agents for films (polyolefin films, etc.), plate-out inhibitors, silicone resin reinforcing agents, rubber reinforcing agents (for tires, general rubbers, etc.), fluidity Improvement materials, anti-caking agents for powdered resins, printability improvers, matting agents for synthetic leather and coating films, fillers for adhesives and adhesive tapes, translucency modifiers, antiglare modifiers, porous用途 Applications such as fillers for polymer sheets.

  Also, for example, in the field of papermaking, thermal paper fillers (such as residue adhesion inhibitors), ink jet paper image fillers (ink absorbers, etc.), diazo photosensitive paper fillers (photosensitive density adjusters, etc.), tracing paper Uses such as a writability improver for coated paper, a filler for coated paper (writeability, ink absorbability, antiblocking improver, etc.), a filler for electrostatic recording, and the like.

Furthermore, in the field of papermaking applications, the molded product of the present invention can be used as humidity control paper for humidity control. Hereinafter, although this humidity control paper is demonstrated, you may use the paper produced with the same method, material, etc. for uses other than humidity control.
Cellulose fibers are used as a base material, and this can be mixed and molded with the silica and binder resin of the present invention to obtain a humidity regulator (resin molded body of the present invention). This is mixed with a solvent to form a slurry, and then the slurry is dehydrated and formed into a semi-humid filter. Thereafter, the semi-humid filter body is dried and solidified to obtain a solidified product. Thereby, humidity control paper is obtained as a molded object of the present invention.

  The humidity control paper is usually composed of 100 parts (parts by weight) of cellulose fibers, 100 to 3000 parts of silica, and 1 to 20 parts of organic binder resin in solid content with respect to 100 parts of silica. preferable. Thereby, it is possible to obtain a humidity control paper having good moldability and excellent humidity control ability.

  The humidity control paper manufacturing method includes, for example, a first mixing step in which cellulose fibers, silica, and water are mixed to form a slurry, and the slurry and an organic binder resin are mixed to form a mixed slurry. 2 mixing step, a forming step of dehydrating and forming the mixed slurry to form a semi-humid filter body, and a drying step of drying and solidifying the semi-moist filter body to form an integral solid.

  Cellulose fibers used here include those exemplified in the description of the base material, and examples of natural cellulose fibers include cotton, Bombax cotton (Kiwata), Kabok and other seed hair fibers, hemp, flax, jute, ramie, mulberry, Ginskin fibers such as mitsumata, leaf fibers such as Manila hemp and New Zealand hemp, coniferous trees (pine, fir, spruce, tsuga, cedar), hardwood (beech, hippopotamus, bopra, maple, etc.) wood fibers, and the like.

  The artificial cellulose fibers include viscose artificial silk, copper ammonia rayon, fortisan, regenerated cellulose fibers such as nitrate human silk, and semisynthetic fibers such as acetate human silk. Furthermore, this cellulose fiber may be obtained from recycled resources such as old newspapers, Chile papers, old magazines and the like. These cellulose fibers preferably have a fiber length in the range of 0.1 mm to several tens of mm. When the fiber length is less than 0.1 mm, the fiber entanglement is insufficient and the moldability is poor. On the other hand, when it exceeds several tens of mm, the fibers and the silica gel are difficult to disperse uniformly, and the specific surface area becomes small, which may reduce the humidity control performance.

  In the humidity control paper, the silica of the present invention is preferably mixed in an amount of 100 to 3000 parts with respect to 100 parts of cellulose fibers. This is because if the amount is less than 100 parts, sufficient ability to absorb moisture in the air may not be obtained. If it exceeds 3000 parts, it may be difficult to maintain a certain shape as a humidity control agent. The binder resin is preferably 1 to 20 parts with respect to 100 parts of silica. In the case of less than 1 part, there is a possibility that a material having sufficient water resistance cannot be obtained. On the other hand, when it exceeds 20 parts, it is difficult to expect sufficient humidity control.

  Moreover, also in humidity control paper, other additives can be mixed to such an extent that the outstanding performance is not impaired like other molded objects. Although there is no restriction | limiting in an additive, As a specific example of a preferable additive, polyvinyl alcohol (PVA), carboxymethylcellulose (CMC), an alumina sol, a silica sol etc. are mentioned as a dispersing agent which improves a dispersibility. Examples of the fibrous reinforcing material include inorganic fibers such as glass fibers and ceramic fibers, or synthetic fibers such as nylon fibers and rayon fibers. Furthermore, a pigment, dye, etc. are mentioned as an additive assistant. Moreover, water glass, cement, gypsum, etc. are raised as a binder for improving strength.

  Next, a method for producing humidity control paper will be exemplified. First, the cellulose fiber, silica and water are mixed to form a slurry (first mixing step). The order of mixing these raw materials is not particularly limited. First, an aqueous slurry of cellulose fibers is prepared by beating cellulose fibers with a beater or the like. Next, the cellulose fiber slurry is mixed with silica prepared by dry pulverization or wet pulverization to an appropriate size and shape. The above mixing method is arbitrary, but is preferably performed using a propeller mixer, a Henschel mixer, a ball mill, a vibration mill, a disper mill, or the like.

  Next, the obtained slurry and the organic binder resin are mixed to obtain a mixed slurry (second mixing step). The mixing ratio of the cellulose fiber, silica, and organic binder resin is the same as described above. In the first or second mixing step, a flocculant such as bangsulphate, acrylamide polymer, and acrylamide-modified polymer may be appropriately mixed for the purpose of improving drainage. Moreover, you may mix suitably additives, such as dye and a pigment.

  Next, the obtained mixed slurry is dehydrated and molded into a desired shape using a papermaking method, a filter press method, a slip cast method, or the like to obtain a semi-humid filter body (molding step). Moreover, it is preferable that the moisture content of the semi-humid filter body obtained by this dehydration and shaping | molding is 50 to 80 weight%. This is because when the water content exceeds 80% by weight, molding in the molding process is difficult, and the shrinkage rate becomes large, and cracks, cracks, etc. may occur in the drying process, resulting in a decrease in strength. It is. Further, when the amount is less than 50% by weight, the bonding force is weak, which is not preferable. In addition, when this moisture content is 55 to 70 weight%, it is more preferable.

  Next, the semi-humid filter body is heated and solidified to obtain an integrally solidified product (drying step). In this drying step, the semi-humid filter is dried by a room temperature drying method, a vacuum drying method, a pressure drying method, a pressure / heat drying method, a vacuum heat drying method, a vacuum freeze drying method, or the like. In this case, the drying may be performed simultaneously with the molding in the molding process. In the above production method, as an additive, a filler may be appropriately mixed for the purpose of improving the strength and improving the appearance. Examples of the additive include kaolin and silica sand. Moreover, you may mix suitably various additives, such as a fungicide, a fragrance | flavor, a pigment, and dye.

  The above humidity control paper has a humidity control function superior to that of the prior art because most of the pores of silica contained therein are open to the outside of the humidity control paper. Therefore, for example, it is used by blending into building materials, wall materials, wallpaper, packaging paper for packaging food, corrugated paper used for transporting food, interior materials for automobiles, wall materials for storage of books and paintings, etc. be able to.

  Returning to the description of the application field of the present invention, for example, in the field of food applications, beer filter aids, soy sauce / sake / wine fermentation product drop agents, various fermented beverage stabilizers (turbidity factor protein and yeast) Removal), food additives, anti-caking agents for powdered foods, and the like.

  In the medical and agrochemical field, for example, tableting aids for pharmaceuticals, grinding aids, dispersion / pharmaceutical carriers (dispersion / sustained release / delivery improvement, etc.), agrochemical carriers (oily agrochemical carrier / hydration dispersibility improvement)菩, sustained release / delivery property improvement), agricultural chemical additives (anti-caking agent / powdering property improving agent, etc.), agricultural chemical additives (anti-caking agent, anti-settling agent, etc.) and the like.

Further, for example, in the field of separation materials, uses such as a chromatographic filler, a separating agent, a fullerene separating agent, an adsorbent (protein, pigment, odor, etc.), a dehumidifying agent and the like can be mentioned.
Further, for example, in the agricultural field, feed additives and fertilizer additives can be mentioned.
Also, for example, in the life-related field, humidity control agents, desiccants, cosmetic additives, antibacterial agents, deodorants / deodorants / fragrances, detergent additives (surfactant powders, etc.), abrasives (for toothpastes, etc.) , Powder fire extinguishing agents (powdering property improvers, anti-caking agents, etc.), antifoaming agents, battery separators and the like.

  Also, for example, in the clothing field, general clothing such as shirts, blouses, pants, jackets, sweaters, blousons, inners and stockings, and sports clothing such as athletic wear and windbreakers are used as moisture conditioning fibers, moisture-absorbing heating fibers, and sustained-release fibers. It can be suitably used for uniforms, work clothes, other hats for dust-proof clothing, and the like.

  Further, the molded article of the present invention is a sustained-release carrier, and is used as an anti-aging agent, curing agent, agricultural chemical, fertilizer, disinfectant, disinfectant, antibacterial agent, insecticide, insecticide, herbicide, aromatic for polymer materials. By supporting chemical substances (pharmaceuticals, etc.) having various functions and actions such as pest repellents, various drugs and physiologically active substances as supported components, these supported components are stored and gradually with time. It can be suitably used as a sustained release agent to be released.

When the shaped article of the present invention is used as a sustained-release carrier and various drugs are supported and used as a sustained-release agent, the drug or the like can be freely selected according to the intended use.
Specific examples include, for example, salicione, marathon, dimethoate, diazinon, diethylamide, 2-ethylthiomethylphenyl = methylcarbamate, thiophosphoric acid, 2-methyl-3-cyclohexene-1-carboxylic acid and the like as agricultural chemical pesticides. It is done.

Examples of the bactericides include copper nonylphenol sulfonate, dineb, anzep, thiuram, polyoxin, and cycloheximide.
Further, for example, herbicides include chloromethoxynyl, nitralin, 3- (3,3-dimethylureido) phenyl = tertiary-butylcarbamate and the like.

For example, hinokitiol is mentioned as an antibacterial agent.
Further, for example, as a pest repellent, a phenolic compound may be mentioned.
Examples of the antioxidant for plastic include bisphenol such as 2,2-bis (4-hydroxydiphenyl) propane, a condensate of cyclohexane, disalicylic resorcin, and phosphite.

Examples of the anti-aging agent include amine compounds such as phenyl-β-naphthylamine, phenol compounds such as styrenated phenol, thiourea derivatives, and benzimidazoles.
Examples of fertilizers include ammonia compounds such as urea, ammonium sulfate, and ammonium nitrate, phosphorus compounds such as lime superphosphate and lime heavy perphosphate, and compounds containing potassium.

  Further, for example, as drugs and physiologically active substances, antihypertensive diuretics, vasodilators, arrhythmia therapeutic agents, cardiotonic agents, hormonal agents, immune regulators, antibiotics, antitumor agents, antiulcer agents, antipyretic agents, analgesics, anti-inflammatory agents And drugs classified into antitussives, sedatives, muscle relaxants, antiepileptics and the like. Specific examples of these pharmaceutical and physiologically active substances include drugs described in the Medical Products Handbook 5th edition (published by Yakuho Hokpo Co., Ltd.) or similar drugs.

  However, the drugs listed above are merely examples, and the drugs that can be held by the sustained-release carrier are not limited thereto.

[VI] Other:
Although the present invention has been described in detail above, the present invention is not limited to the above description and can be implemented with appropriate modifications.
For example, the usage forms of the composition, molded article, and paint of the present invention are not limited to those described above, and can of course be used in other applications and forms.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention can be arbitrarily changed and implemented in the range which does not deviate from the summary, without being restrict | limited to a following example. In the present specification, “parts” means “parts by weight” unless otherwise specified.

(1) Analytical method (1-1) Pore volume, specific surface area About a sample, BET nitrogen adsorption isotherm (isothermal desorption curve) was measured by AS-1 manufactured by Cantachrome, and pore volume (ml / g). , Specific surface area (m ² / g), mode pore diameter D _max (nm), and ratio (%) of pore volume of mode pore diameter D _max ± 20% to the total pore volume It was. Specifically, the pore volume is a value when the relative pressure P / P ₀ = 0.98, and the specific surface area is 3 points of P / P ₀ = 0.1, 0.2, 0.3. It calculated using the BET multipoint method from the nitrogen adsorption amount.

For those having a mode pore diameter (D _max ) of 5 nm or less, the HK method or SF method known to those skilled in the art, and for those having a mode diameter of 5 nm or more by the BJT method, the pore distribution curve and mode The differential pore volume at the pore diameter (D _max ) was determined. The interval between the points of the relative pressure to be measured was 0.025.

(1-2) Powder X-ray diffraction Using a RAD-RB apparatus manufactured by Rigaku Corporation, the powder X-ray diffraction pattern of the sample was measured using CuKa as a radiation source. The measurement conditions were a diverging slit 1/2 deg, a scattering slit 1/2 deg, and a light receiving slit 0.15 mm.

(1-3) Content of metal impurities 15 ml of hydrofluoric acid was added to 2.5 g of the sample and heated to dryness, and then water was added to make 50 ml. ICP emission analysis was performed using this aqueous solution. Sodium and potassium were analyzed by flame flame light method.

(1-4) Solid-state Si-NMR measurement Using a Bruker solid-state NMR apparatus (MSL300), using a sample tube with a resonance frequency of 59.2 MHz (7.05 Tesla) and 7 mm, CP / MAS (Cross Polarization) / Magic Angle Spining) Measured under probe conditions.
Specific measurement conditions are shown in Table 2 below.

Analysis of measured data (Q ⁴ Determination of the peak position) is performed by a method of extracting each peak by the peak division. Specifically, waveform separation analysis using a Gaussian function is performed. For this analysis, waveform processing software “GRAMS386” manufactured by Thermogalatic Co. can be used.
Thereby, the value of Q ⁴ / Q ³ was calculated.

(2) Method for measuring pore volume of silica released to the outside of the molded article of the present invention In the same manner as the analysis method described in (1-1), only the silica contained in the molded article of the present invention is finely divided. Pore volume Vp (ml / g), pore volume Vq (ml / g) of the molded article of the present invention, mode pore diameter D _max (nm) of the molded article of the present invention, and mode pore diameter D _The ratio (%) of the pore volume of _max ± 20% to the total pore volume, and the pore volume Vr (ml / g) of a molded article produced in the same manner except that silica is not contained are obtained.

Next, assuming that the weight ratio of silica in the molded body of the present invention is a%, the weight ratio of those other than silica is b%, and a + b = 100, The pore volume S is determined.
S = (Vq−Vr × b / 100) × 100 / a Formula 1

Moreover, the ratio T (%) of the pore volume of the silica opened to the outside of the molded body of the present invention can be obtained by the following calculation formula 2.
T = (S / Vp) × 100 Formula 2

(3) Example 1
(Method for producing silica)
1000 g of pure water was charged into a 5 L separable flask (with a jacket), which was a glass mold and was equipped with a water-cooled condenser open to the atmosphere at the top. While stirring at 80 rpm, 1400 g of tetramethoxysilane was charged into this over 3 minutes.

  The water / tetramethoxysilane molar ratio is about 6/1. Warm water of 50 ° C. was passed through the jacket of the separable flask. Stirring was continued, and the stirring was stopped when the contents reached the boiling point. Subsequently, hot water of 50 ° C. was passed through the jacket for about 0.5 hour to gel the sol produced.

  Thereafter, the gel was quickly taken out and pulverized through a nylon net having an opening of 600 microns to obtain a powdery wet gel (silica hydrogel). 450 g of this hydrogel and 450 g of pure water were charged into a 1 L glass autoclave and hydrothermally treated at 170 ° C. After hydrothermal treatment for 3 hours, the liquid was cut through a nylon mesh having an opening of 100 microns, and the filter cake was dried under reduced pressure at 150 ° C. until it became a constant weight without washing with water.

The obtained silica gel (silica of the present invention) was pulverized with a pulverizer (Hosokawa Micron AFG-200 type), and powder with an average particle diameter of 5 μm (silica gel with an average particle diameter of 5 μm) was obtained by aerodynamic classification.
The silica gel powder having an average particle size of 5 μm was pulverized by a wet pulverizer {Mitsui Mine SC Mill (SC-50 type)} to obtain a silica gel slurry having an average particle size of 1 μm (silica gel having an average particle size of 1 μm). .
Furthermore, the hydrothermal treatment temperature was changed to 200 ° C., and the pulverization was performed with a Mitsui Mining Fine Mill (SF-30 type), in the same manner as the method for preparing silica gel with an average particle diameter of 5 μm. A powder having an average particle diameter of 2 μm (silica gel having an average particle diameter of 2 μm) was obtained.
When the obtained powder and the dried solid product of the slurry were observed with a scanning electron microscope, these particles were all crushed particles having a fracture surface.

About the obtained silica gel, the pores with the most frequent pore diameter (nm), the pore volume (ml / g), the specific surface area (m ² / g), and the most frequent pore diameter (D _max ) ± 20%, respectively. Table 3 shows the ratio (%) of the volume to the total pore volume, and the measurement results of Q ⁴ / Q ³ .
Further, no crystalline peak appeared in the powder X-ray diffraction diagram, and no peak on the low angle side (2θ ≦ 5 deg) due to the periodic structure was observed.

  The impurity concentration of the obtained silica gel was 1 ppm or less for all of sodium, potassium, calcium, magnesium, titanium, and chromium except that 2 ppm each of iron and aluminum were detected.

(Production of molded body)
A solution (paint of the present invention) formulated so that the ratio of silica to solid content (binder resin + silica) was 60% by weight was applied to a PET film (base material, sheet) using a bar coater # 30. The solution was prepared by mixing 0.8 g of a binder resin emulsion (solid content 50% by weight: 0.4 g of binder resin), 3.6 g of water, and 0.6 g of silica gel having an average particle size of 5 μm.

  Boncoat CG-5010 (Dainippon Ink & Chemicals, Inc., acrylic urethane emulsion) was used as the binder resin emulsion. In addition, the glass transition temperature Tg of acrylic urethane which is binder resin is 30 degreeC.

The coated PET film was dried with a vacuum dryer at 80 ° C. Thereby, the coating film as a molded object of this invention was formed in the PET film surface.
For this coating film, the total pore volume of the mode pore diameter (nm), pore volume (ml / g), specific surface area (m ² / g), mode pore diameter (D _max ) ± 20% The ratio (%) to the pore volume and the ratio T (%) of the pore volume of silica released to the outside of the PET film (molded article of the present invention) on which the coating film was formed were measured. The measurement results are shown in Table 4 together with Q ⁴ / Q ³ of the silica used.

  A liquid crystal thermometer was attached to the PET film to which the paint was applied, and the PET film was placed in a small environmental tester (ESPECSH240) having a relative humidity of 90%.

  Moreover, when the PET film coated with the paint was immersed in a limonene solution in an amount corresponding to the pore volume of silica and the sustained release property was confirmed at room temperature, the smell of limonene was confirmed even after one week. In contrast, when the same limonene solution was immersed in a normal cloth, the limonene scent disappeared in one day.

  From the above results, silica and binder resin are mixed with a solvent, applied to a base material, and then the solvent is removed to produce a molded body in which 30% or more of the pore volume of silica is open to the outside. It was confirmed that it was possible. Furthermore, it was confirmed that the molded body of the present invention exhibits high moisture absorption exothermic property and sustained release property. Further, as described above, since the observed temperature rise is considered to be caused by the heat of adsorption of water, it is considered that a large amount of water is adsorbed to the molded body of the present invention. The body is excellent in absorption and release performance and can be expected to have high humidity control.

(4) Example 2
In the same manner as in Example 1, silica gel (silica of the present invention) having an average particle diameter of 5 μm was produced. Subsequently, the obtained silica gel having an average particle diameter of 5 μm was mixed with water to obtain a silica slurry having a solid content of 10% by weight.
160 g of a mixed solution of a binder resin and water so that the silica slurry has a weight ratio of silica gel: binder resin = 3: 1, and the coating amount with respect to the base material is 3 wt% silica and 1 wt% binder resin. The mixture was mixed to obtain a coating solution (paint), and this was impregnated with cotton (fiber) as a base material. As the binder resin, an acrylic emulsion {Mitsubishi Rayon Co., Ltd. DIANAL LX-100} was used.

After impregnation, the base cotton was drawn with a drawing rate of 150% and then dried at 110 ° C. to produce a molded body. The drawing rate is “squeezing rate = (weight of coating solution impregnated on base material / weight of base material) × 100”.
It is a value defined by.
Next, with respect to the produced molded body, pores having a mode pore diameter (nm), a pore volume (ml / g), a specific surface area (m ² / g), and a mode pore diameter (D _max ) ± 20%. The ratio (%) of the volume to the total pore volume and the ratio T (%) of the pore volume of the silica opened to the outside of the molded body of the present invention were measured. The measurement results are shown in Table 5 together with Q ⁴ / Q ³ of the silica used.

(5) Example 3
A molded body was prepared in the same manner as in Example 2 except that acrylic emulsion {Dainippon Ink & Chemicals, Inc. Boncoat CG-5010} was used as the binder resin. (Nm), pore volume (ml / g), specific surface area (m ² / g), mode pore diameter (D _max ) ± 20% of pore volume in total pore volume (%), And the ratio T (%) of the pore volume of the silica open | released outside the molded object of this invention was measured. The measurement results are shown in Table 5 together with Q ⁴ / Q ³ of the silica used.

(6) Example 4
Except for using a silicone emulsion {Kitahiro Chemical Co., Ltd. TF-3500} as the binder resin, a molded body was prepared in the same manner as in Example 2, and the most frequent pore diameter (nm), Pore volume (ml / g), specific surface area (m ² / g), mode pore diameter (D _max ) ± 20% of pore volume in total pore volume (%), and the present invention The ratio T (%) of the pore volume of silica released to the outside of the molded body was measured. The measurement results are shown in Table 5 together with Q ⁴ / Q ³ of the silica used.

(7) Example 5
Other than using a urethane emulsion {Daiichi Seika Kogyo Co., Ltd. Resamine D-2020} and a cross-linking agent {Daiichi Seika Kogyo Co., Ltd. Resamine D-54 5% mixed with urethane emulsion weight} as the binder resin Then, a molded body was prepared in the same manner as in Example 2, and the modest pore diameter (nm), pore volume (ml / g), specific surface area (m ² / g), and modest size were measured. The ratio (%) of the pore diameter (D _max ) ± 20% to the total pore volume and the ratio T (%) of the pore volume of the silica opened to the outside of the molded body of the present invention. It was measured. The measurement results are shown in Table 5 together with Q ⁴ / Q ³ of the silica used.

(8) Comparative Example 1
A molded product in the same manner as in Example 4 except that silica gel pulverized to a particle size of 2 μm by a fine mill (that is, silica gel similar to silica gel having an average particle size of 2 μm prepared in Example 1) was used as silica particles. And the molded body thus produced had a mode pore diameter (nm), a pore volume (ml / g), a specific surface area (m ² / g), and a mode pore diameter (D _max ) ± 20%. The ratio (%) of the pore volume to the total pore volume and the ratio T (%) of the pore volume of the silica opened to the outside of the molded body of the present invention were measured. The measurement results are shown in Table 5 together with Q ⁴ / Q ³ of the silica used.

(9) Comparative Example 2
A molded body was produced in the same manner as in Example 4 except that silica gel pulverized to 1 μm by an SC mill (that is, silica gel similar to silica gel having an average particle diameter of 1 μm prepared in Example 1) was used as silica particles. For the formed article, the pores with the most frequent pore diameter (nm), the pore volume (ml / g), the specific surface area (m ² / g), and the most frequent pore diameter (D _max ) ± 20% The ratio (%) of the volume to the total pore volume and the ratio T (%) of the pore volume of the silica opened to the outside of the molded body of the present invention were measured. The measurement results are shown in Table 5 together with Q ⁴ / Q ³ of the silica used.

From Examples 2 to 5 and Comparative Examples 1 and 2 , silica and binder resin are mixed with a solvent, impregnated into a base material, and then the solvent is removed, so that 30% or more of the pore volume of silica is exposed to the outside. It was confirmed that an open molded body can be produced.

  Further, the molded body produced in Example 4 was subjected to a moisture absorption experiment using a small environmental tester (ESPEC SH240). Specifically, the molded body produced in Example 4 was absorbed for 24 hours in a system at a temperature of 20 ° C. and a humidity of 65% for 24 hours, and then absorbed in a system of a temperature of 30 ° C. and a humidity of 90% for 15 minutes, and the moisture absorption rate was measured. did. Thereafter, the second measurement was further performed under the same conditions, and the second moisture absorption amount was divided by the weight of the entire molded body to obtain the moisture absorption rate.

  Whereas the moisture absorption rate of only cotton measured under the same conditions is 4.1% by weight, the moisture absorption rate of a molded product produced by impregnating cotton with a coating solution measured here is 5.5% by weight. Met. Thereby, it was confirmed that the molded object of this invention shows high hygroscopicity.

  In addition, the molded body produced in Example 4 and the unprocessed cotton used in Example 4 were subjected to washing treatment (operation cycle of washing, dehydration, rinsing, dehydration, rinsing, dehydration) in a fully automatic washing machine for home use. Carried out. As a laundry detergent, an attack made by Kao Corporation was used, and the washing temperature was room temperature. These were dried at room temperature for 3 hours, and ten persons smelled and compared the fragrance strength of the cloth. As a result, all 10 persons determined that the molded body of Example 4 had a stronger scent. Moreover, when 10 people smelled similarly after 5 hours, all 10 persons determined that there was residual scent.

  Furthermore, the molded body produced in Example 4 and the unprocessed cotton used in Example 4 were mixed into an aqueous solution prepared so that the commercially available soft finish (Humming flare manufactured by Kao Corporation) was 0.03%. After soaking, it was dehydrated in a washing machine. These were dried at room temperature for 3 hours, and ten persons smelled and compared the fragrance strength of the cloth. As a result, all 10 persons determined that the molded body of Example 4 had a stronger scent. Moreover, when 10 people smelled similarly after 5 hours, all 10 persons determined that there was residual scent.

Further, the molded bodies produced in Example 4 and Comparative Examples 1 and 2 were each washed 10 times using a HITACHI fully automatic electric washing machine {White Promise 60 (NW-6CY)} {each wash: 6 minutes, Rinse: twice, dehydration: 3 minutes, amount of water: 25 L, detergent (Kao Attack) 16.7 g, co-washing: 7 new T-shirts}, TG-DTA6300 type manufactured by Seiko Instruments Inc. Using a platinum pan: 200 ml / min under air), an experiment for measuring the remaining amount of silica gel was performed.
As a result, the silica gel residual ratio before and after washing was 51% for the molded body produced in Example 4, 61% for the molded body produced in Comparative Example 1 , and 59% for the molded body produced in Comparative Example 2 . From this, it was confirmed that the molded article of the present invention has sufficient washing durability.

  The resin molded body, resin composition, and paint of the present invention are a building material use field, a catalyst use field, an air conditioning field, a paint / ink field, a resin additive use field, a papermaking use field, a food use field, a medical pesticide field, It can be used in various fields such as a separation material field, an agricultural application field, a life-related field, and a clothing field.

Claims (5)

A resin molding comprising at least a binder resin and silica,
63 % or more of the pore volume of the silica is open to the outside of the resin molded body ,
The resin molded product , wherein the silica satisfies the following conditions (a) to (f) .
(A) The pore volume of the silica is 0.3 ml / g or more and 3.0 ml / g or less.
(B) The specific surface area of the silica is 100 m ² / g or more and 1000 m ² / g or less.
(C) The mode pore diameter of the silica is 2 nm or more and 50 nm or less.
(D) the average particle diameter of the silica exceeds 2 μm, and the total volume of pores in the range of ± 20% of the value of the most frequent pore diameter (D _max ) is 50% or more of the total volume of all the pores .
In the solid Si-NMR measurement of (e) the silica, -OSi are three bonded Si ^{(Q 3)} and -OSi of ^Q 4 / ^{Q 3} in which a molar ratio of four bonded Si ^{(Q 4)} The value is 1.4 or more.
(F) The silica is obtained by hydrolyzing silicon alkoxide and hydrothermally treating it. And further comprising a substrate,
The resin molded article according to claim 1, wherein the silica is fixed to at least a part of the base material by the binder resin. The resin molded body according to claim 2 , wherein the base material comprises at least a fiber . The resin molded body according to any one of claims 1 to 3 , wherein the binder resin has a glass transition temperature of -80 ° C or higher and 110 ° C or lower .   The resin molded body is obtained by mixing the binder resin, the silica, and a solvent and removing the solvent, and the binder resin becomes a colloid in the solvent to form an emulsion.
The resin molded product according to any one of claims 1 to 4, wherein