TW201731766A - Method for producing liquid that contains pulverized gel - Google Patents

Abstract

The purpose of the invention is to provide a method for producing a highly homogeneous liqud that contains pulverized gel. This method for producing a liquid that contains pulverized gel includes a gel production step for producing a gel, a solvent substitution step for substituting another solvent for the solvent in the gel, and a gel pulverization step for pulverizing the gel in the other solvent, the method for producing a gel that contains pulverized gel being characterized in that the pulverization step is conducted in a plurality of separate pulverization stages, a concentration adjustment step for adjusting the concentration of the liquid that contains the gel is included after the solvent substitution step and before the beginning of the first pulverization stage, and the concentration of the liquid that contains the gel is not adjusted after the beginning of the first pulverization stage.

Description

Method for producing gel-containing pulverized liquid

The present invention relates to a method of producing a gel-containing pulverized liquid.

A gel-containing pulverized liquid in which a porous structure such as a ruthenium oxide compound material (ruthenium compound material) is used as a raw material to form a void structure has been in progress. For example, an example of the method for producing a gel-containing pulverized liquid is a simultaneous gelation of a porous body such as a cerium oxide compound (gelation step), and the gelled porous body (porous body condensed) Glue) pulverization (pulverization step). Then, a void structure is formed by coating the gel-containing pulverized liquid produced as described above. The void structure can be applied to various objects, for example, as a void layer, and can be suitably applied to an optical member or the like.

The pulverization step of the prior art is disclosed, for example, in Patent Document 1 and Non-Patent Document 1, and the porous body gel is pulverized in one step by ultrasonic treatment. Prior Technical Literature Patent Literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-11175 Non-patent literature

Non-Patent Document 1: J. Mater. Chem., 2011, 21, 14830-14837

Problem to be Solved by the Invention The gel produced by the gelation step described above is, for example, in a state of a block. Therefore, for example, by performing the pulverization step as in Patent Document 1, the pulverized gel is easily mixed with the solution in the mixing step. This makes it easier to manufacture a gel-containing liquid.

On the other hand, in recent years, it has been desired to pursue a gel-containing pulverized liquid which is extremely excellent in uniformity.

However, in the production of the gel-containing pulverized liquid, especially in the mass production of industrial specifications, the single-stage gel pulverization operation tends to make the pulverized gel particle size uneven. Then, in order to make the particle diameter of the gel-pulverized material uniform, a method of performing gel pulverization in multiple stages (complex stages) was conceived. Further, in order to stabilize the quality of a product (for example, a void layer, an optical member, etc.) using a gel-containing pulverized liquid, it is necessary to make the concentration of the gel-containing pulverized liquid uniform.

However, when the concentration is adjusted while performing multi-stage pulverization, the gel and the solvent may be uniformly mixed and become uneven. For example, in the case where the concentration adjustment is performed in the coarse pulverization stage earlier than the final pulverization stage, since the particle size of the gel pulverized material is large (coarse), it is difficult to uniformly mix the gel-containing liquid. Therefore, in order to achieve homogenization of the gel and the solvent, it is necessary to perform coarse pulverization during the concentration adjustment. Further, it is difficult to adjust the concentration after the final pulverization (for example, nano pulverization, which pulverizes the gel particles to a nanometer-sized particle size). Specifically, the gel-containing pulverized liquid after the final pulverization stage tends to have a high concentration. However, if the concentration is increased after the final pulverization stage, the particle size of the gel pulverized material is small and the particles are agglomerated. Further, even if the concentration is to be low after the final pulverization stage, the original concentration is higher than the final target concentration, so that the viscosity is too high, and clogging may occur in the pulverization step device, which may make pulverization difficult.

Accordingly, an object of the present invention is to provide a method for producing a gel-containing pulverized liquid which is extremely excellent in uniformity. Means to solve the problem

In order to achieve the above object, a method for producing a gel-containing pulverized liquid of the present invention is characterized by comprising the steps of: a gel production step of producing a gel, a solvent replacement step of replacing a solvent in the gel with another solvent, and a gel pulverizing step of pulverizing the gel in the other solvent; the manufacturing method is performed by dividing the pulverizing step into a plurality of pulverizing steps, and further including a concentration adjustment after the solvent replacing step and before the start of the initial pulverizing step In step, the concentration adjustment of the gel-containing liquid is performed, and the concentration adjustment of the gel-containing liquid is not performed immediately after the start of the initial pulverization stage. Effect of the invention

According to the method for producing a gel-containing pulverized liquid of the present invention, the pulverization step is divided into a plurality of pulverization steps as described above, and the concentration adjustment of the liquid containing the gel is not performed after the start of the first pulverization stage. Therefore, even in the mass production of industrial specifications, it is possible to produce a gel-containing pulverized liquid which is extremely excellent in uniformity.

The following examples are given to further illustrate the invention. However, the invention is not limited by the following description.

The method for producing a gel-containing pulverized liquid of the present invention is carried out by dividing the pulverization step for pulverizing the gel into a plurality of pulverization stages as described above. The number of the aforementioned pulverization stages is not particularly limited, and may be, for example, two stages or three stages or more.

In the method for producing a gel-containing pulverized liquid of the present invention, for example, the plurality of pulverization stages may include a first pulverization stage and a second pulverization stage for pulverizing the gel, wherein the first pulverization stage is The gel is pulverized into particles having a volume average particle diameter of 0.5 to 100 μm, and the second pulverization step is a step of further pulverizing the particles into particles having a volume average particle diameter of 10 to 1000 nm after the first pulverization step. Further, in this case, the plurality of pulverization stages may or may not include the pulverization stage other than the first pulverization stage and the second pulverization stage.

In the present invention, the shape of the "particles" (for example, particles of the pulverized material of the gel) is not particularly limited, and may be, for example, a spherical shape or an aspherical system. Further, in the present invention, the particles of the pulverized material may be, for example, sol-gel rosary particles, nano particles (hollow nano cerium oxide, nano balloon particles), or nano fibers.

In the present invention, for example, the gel is preferably a porous gel, and the pulverized material of the gel is preferably porous, but is not limited thereto.

In the present invention, the gel-pulverized material may be composed of, for example, a structure having at least one of a particle shape, a fiber shape, and a flat shape. The constituent elements of the particulate form and the flat shape may be made of, for example, an inorganic material. Further, the constituent elements of the particulate constituent unit may contain, for example, at least one element selected from the group consisting of Si, Mg, Al, Ti, Zn, and Zr. The structure in which the particles are formed (constituting unit) may be solid particles or hollow particles, and specifically may be, for example, polyfluorene oxide particles or polycrystalline oxygen particles having fine pores, hollow cerium oxide nanoparticles or cerium oxide nanoparticles. Balloons, etc. The fibrous constituent unit is, for example, a nanofiber having a diameter of a nanometer, and specifically, a cellulose nanofiber or an alumina nanofiber. The flat constituent unit is, for example, a nano-clay, and specifically, a nano-sized benton (for example, Kunipia F [trade name]). The fibrous constituent unit is not particularly limited, and may be selected from the group consisting of carbon nanofibers, cellulose nanofibers, alumina nanofibers, chitin nanofibers, and chitin nanofibers. At least one fibrous substance in the group consisting of nanofibers, glass nanofibers, and cerium oxide nanofibers.

In the production method of the present invention, the plurality of pulverization stages (for example, the first pulverization stage and the second pulverization stage) are carried out as described above in the "other solvent". In addition, the detailed description of the "other solvent" mentioned later is mentioned later.

In addition, the "solvent" (for example, a solvent for producing a gel, a solvent for producing a void-constituting film, a solvent for replacement, etc.) in the present invention may be dissolved in a gel or a pulverized product thereof, for example, the gel or the gel thereof The pulverized material or the like is dispersed or precipitated in the aforementioned solvent.

After the first pulverization stage, the volume average particle diameter of the gel may be, for example, 0.5 to 100 μm, 1 to 100 μm, 1 to 50 μm, 2 to 20 μm, or 3 to 10 μm. After the second pulverization stage, the volume average particle diameter of the gel may be, for example, 10 to 1000 nm, 100 to 500 nm, or 200 to 300 nm. The volume average particle diameter is a particle size deviation of the pulverized material in the gel-containing liquid (gel-containing liquid). The volume average particle diameter can be measured by, for example, a particle size distribution analyzer such as a dynamic light scattering method or a laser diffraction method, an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

Further, immediately after the first pulverization step, the shear viscosity of the liquid may be, for example, 50 mPa/s or more, 1000 mPa∙s or more, 2000 mPa∙s or more, or 3000 mPa∙s or more at a shear rate of 10001/s. For example, it may be 100 Pa ∙ s or less, 50 Pa ∙ s or less, or 10 Pa ∙ s or less. Immediately after the second pulverization step, the shear viscosity of the liquid may be, for example, 1 mPa ∙ s or more, 2 mPa ∙ s or more, or 3 mPa ∙ s or more, and may be, for example, 1000 mPa ∙ s or less, 100 mPa ∙ s or less, or 50 mPa ∙ s. the following. In addition, the method of measuring the shear viscosity is not particularly limited, and can be measured, for example, by using a vibrating viscosity measuring machine (trade name: FEM-1000V, manufactured by Sekonic Co., Ltd.) as described in the examples below.

After the first pulverization stage, for example, the shear viscosity of the liquid containing the particles may be 50 mPa ∙ s or more, and the volume average particle diameter of the particles may be 0.5 to 50 μm.

In the method for producing a gel-containing pulverized material of the present invention, the gel concentration of the liquid containing the gel can be adjusted to, for example, 1% by weight or more, 1.5% by weight or more, 1.8% by weight or more, or 2.0 in the concentration adjusting step. The weight% or more or 2.8% by weight or more may be adjusted to, for example, 5% by weight or less, 4.5% by weight or less, 4.0% by weight or less, 3.8% by weight or less, or 3.4% by weight or less. In the concentration adjustment step, the gel concentration of the liquid containing the gel may be adjusted to, for example, 1 to 5% by weight, 1.5 to 4.0% by weight, 2.0 to 3.8% by weight, or 2.8 to 3.4% by weight. From the viewpoint of ease of handling of the gel pulverization step, the aforementioned gel concentration should not be too high to prevent the viscosity from becoming too high. Moreover, from the viewpoint of use as a coating liquid to be described later, the gel concentration should not be too low to prevent the viscosity from becoming too low. The gel concentration of the liquid containing the gel can be, for example, the weight of the liquid and the weight of the solid component (gel) after subtracting the solvent of the liquid, and the measurement of the latter is excluded from the measurement of the former. Calculated.

Further, in the concentration adjustment step, for example, in order to appropriately adjust the gel concentration of the liquid containing the gel, the concentration can be lowered by adding a solvent or the concentration can be increased by volatilizing the solvent. Or, the concentration adjustment step, for example, if the gel concentration of the liquid containing the gel is determined to be an appropriate gel concentration, the operation of lowering the concentration or increasing the concentration (concentration adjustment) may not be performed. The liquid containing the gel is sent directly to the next step. Or, in the foregoing concentration adjustment step, for example, if the gel concentration of the liquid containing the gel is not determined, the determination and the concentration adjustment may not be performed, and the liquid containing the gel may be directly sent. Go to the next step.

In the gel pulverization step, the weight % concentration change of the liquid containing the gel may be, for example, within ±3% or within ±2.8% from the beginning of the first pulverization phase to the end of the final pulverization phase. Within ±2.6%, within ±2.4% or within ±2.2%.

In the method for producing a gel-containing pulverized material of the present invention, it is preferable to further include a gel form controlling step before the solvent replacement step to control the shape and size of the gel. In the gel form control step described above, it is preferred to control so that the gel size does not become too small. Since a large amount of solvent can be attached around the finely pulverized gel, there is a problem that the measurement of the solvent concentration is lower than the actual concentration, the solvent remains higher than the actual concentration, and the measurement deviation value is high, so if the gel size is not It is easy to avoid such problems when they become too small. Further, since the gel size is not too large before the solvent replacement step, the solvent replacement efficiency is good. Further, after the gel form control step, it is preferred to control the size of each gel to a nearly uniform state. This is because if the size of each gel is nearly uniform, it is possible to suppress the difference in the particle size and the gel concentration of the gel-pulverized material between the batches of the gel-containing pulverized liquid, and it is easy to obtain a coagulation excellent in uniformity. Gum pulverized liquid.

In the gel form control step, the short diameter of the gel may be controlled to, for example, 0.5 cm or more, 0.6 cm or more, 0.7 cm or more, or 0.8 cm or more, or may be controlled to, for example, 15 cm or less, 13 cm or less, 10 cm or less, or 8 cm. the following. Further, in the gel form control step, the long diameter of the gel may be controlled to, for example, 30 cm or less, less than 30 cm, 28 cm or less, 25 cm or less, or 20 cm or less, or may be controlled to, for example, 1 cm or more, 2 cm or more, or 3 cm or more. , 4cm or more or 5cm or more. Further, in the present invention, the "short diameter" of the three-dimensional object (the third dimension) means the length measured at the position where the length is the shortest among the possible positions at which the length of the three-dimensional object can be measured. Further, in the present invention, the "long diameter" of the three-dimensional object (the ternary body) means the length measured at the position where the length is the longest at a position at which the length of the three-dimensional object can be measured.

After the gel morphology control step, the shape of the gel is not particularly limited, and can be controlled, for example, to a rectangular parallelepiped (including a cube), a cylindrical shape, a polygonal three-dimensional object (for example, a triangular column, a hexagonal column, or the like), a spherical shape, or Elliptical balls (such as the shape of a football), etc. After the gel form control step, it is preferable that the shape of the gel is controlled to be a simple square or a shape close to a rectangular parallelepiped. In the gel form control step, when the gel is controlled to grow into a rectangular parallelepiped, the short side can be controlled, for example, to 0.5 cm or more, 0.6 cm or more, 0.7 cm or more, or 0.8 cm or more, and can be controlled to, for example, 15 cm or less. 13 cm or less, 10 cm or less, or 8 cm or less. Further, in the gel form control step, when the gel is controlled to grow into a rectangular shape, the long side can be controlled, for example, 30 cm or less, less than 30 cm, 28 cm or less, 25 cm or less, or 20 cm or less, and can be controlled, for example, at 1 cm. Above, 2 cm or more, 3 cm or more, 4 cm or more, or 5 cm or more. Further, in the present invention, the "short side" of the rectangular parallelepiped means the shortest side, and the "long side" means the longest side.

The gel morphology control step may be carried out, for example, after the gel production step, or may be carried out in the gel production step (concurrently with the gel production step). More specifically, it is as described below.

In the gel form control step, for example, the gel may be cut in a state in which the gel is fixed, thereby controlling the gel to be controlled into the three-dimensional object. In the case where the brittleness of the gel is extremely high, the gel may not uniformly disintegrate regardless of the cutting direction when the gel is cut. Therefore, by fixing the periphery of the gel, the pressure in the compression direction at the time of cutting is uniformly applied to the gel itself, so that the gel can be uniformly cut in the cutting direction. For example, the gel shape before the solvent replacement step may be a nearly rectangular parallelepiped, and in the gel form control step, five of the six faces of the gel surface of the near cuboid are in contact with other substances, thereby allowing When the gel is fixed and the remaining one surface is exposed, the gel is inserted into the cutting jig from the exposure to cut the gel. The cutting jig is not particularly limited, and examples thereof include a cutter, a wire-shaped jig, and a thin and profitable plate-shaped jig. Further, the cutting of the gel can be carried out, for example, in the other solvent described above.

Further, for example, in the gel production step, the gel may be solidified in a mold (container) corresponding to the shape and size of the three-dimensional object to control the gel into the three-dimensional object. Thereby, even when the brittleness of the gel is extremely high, since the gel can be controlled to a predetermined shape and size without cutting the gel, it is possible to avoid gelation and cutting when the gel is cut. A situation in which the direction of the fracture is unevenly disintegrated.

Further, in the method for producing a gel-containing pulverized liquid of the present invention, for example, the liquid containing the gel (liquid containing gel) can be measured after the end of the first pulverization stage and before the end of the final pulverization stage. The gel concentration, and only the aforementioned liquid having the aforementioned gel concentration within a predetermined number of enthalpy is supplied to the subsequent pulverization stage. Further, it is necessary to form a uniform liquid when measuring the gel concentration. Therefore, after the completion of the pulverization step, it is preferred to form a liquid having a high degree of viscosity and not being easily separated by solid-liquid. As described above, from the viewpoint of ease of handling of the gel-containing liquid, the gel concentration should not be too high to avoid excessive formation of a high viscosity; and from the viewpoint of use as a coating liquid, the gel concentration should not be too low. So as not to form too low viscosity. From such a viewpoint, only the liquid having the gel concentration within a predetermined number of enthalpy can be supplied to the final pulverization stage. The predetermined range of the gel concentration is, for example, 2.8 wt% or more and 3.4 wt% or less as described above, but is not limited thereto. Further, the gel concentration measurement (concentration management) may be performed after the completion of the first pulverization stage and before the end of the final pulverization stage, or may be added or replaced, after the solvent replacement step and the condensate Either or both of the gum pulverization step and the final pulverization stage (for example, the aforementioned second pulverization stage) are carried out. Therefore, after the gel concentration is measured, for example, only the liquid having the gel concentration within a predetermined number of enthalpy is supplied to the pulverization stage after the pulverization, or is used as a finished product of the gel-containing pulverized liquid. Come to supply. Further, when the gel concentration is measured before the gel pulverization step after the solvent replacement step, the concentration adjustment step may be performed as needed.

Further, in the concentration management before the gel pulverization step after the solvent replacement step, since the amount of the solvent attached to the gel is unstable, the concentration measurement 偏差 each measurement deviation value may become large. Therefore, it is preferable to control the shape and size of the gel to a nearly uniform state by the gel form control step before the concentration management before the gel pulverization step after the solvent replacement step. Thereby, the concentration measurement can be performed stably. Further, for example, it is also possible to manage the gel concentration of the liquid containing the gel in a uniform manner with high precision.

In the production method of the present invention, at least one of the plurality of pulverization stages is preferably a pulverization method different from the other at least one pulverization stage. The pulverization method in the plurality of pulverization stages may be all different, but may be a pulverization stage performed in the same pulverization method. For example, in the case where the plurality of pulverization stages are three stages, all of the three stages may be carried out in different manners (that is, in three kinds of pulverization methods), or in any two pulverization stages in the same pulverization manner, and only one pulverization is performed. The stages are carried out in different smashing ways. Further, the pulverization method is not particularly limited, and examples thereof include a cavitation method and a non-media method, which will be described later.

In the production method of the present invention, the gel-containing pulverized material liquid system is, for example, a sol liquid, and contains particles (pulverized material particles) obtained by pulverizing the gel.

In the method for producing a gel-containing pulverized material liquid according to the present invention, the plurality of pulverization stages may include a coarse pulverization stage and a main pulverization stage, and after obtaining the bulk sol particles through the coarse pulverization stage, the pores are maintained through the main pulverization stage. Sol particles of a gel network.

In the production method of the present invention, for example, after at least one of the plurality of stages of the pulverization stage (for example, at least one of the first pulverization stage and the second pulverization stage), further comprising: grading the gel particles Grading step.

The production method of the present invention includes, for example, a gelation step of gelatinizing a bulk porous body in a solvent to form the gel. At this time, for example, in the first pulverization stage (for example, the first pulverization stage) in the multi-stage pulverization stage, the gel geled by the gelation step is used.

The manufacturing method of the present invention comprises, for example, a ripening step of aging the gelled gel in a solvent. At this time, for example, in the first pulverization stage (for example, the first pulverization stage) in the multi-stage pulverization stage, the gel after the aging step is used.

In the production method of the present invention, for example, the solvent replacement step is carried out after the gelation step, and the solvent is replaced with another solvent. At this time, for example, in the first pulverization stage (for example, the first pulverization stage) in the multistage pulverization stage, the gel in the other solvent described above is used.

In the production method of the present invention, at least one of the multi-stage pulverization stages (for example, at least one of the first pulverization stage and the second pulverization stage) controls the porous body while measuring the shear viscosity of the liquid, for example. The crushing of the body.

In the production method of the present invention, at least one of the multi-stage pulverization stages (for example, at least one of the first pulverization stage and the second pulverization stage) is performed by, for example, high-pressure medium-free pulverization.

In the production method of the present invention, the gel is, for example, a gel of a ruthenium compound containing at least a trifunctional or lower saturated bond functional group.

In addition, the gel-containing pulverized liquid obtained by the method for producing a gel-containing pulverized liquid of the present invention may be referred to as "the gel-containing pulverized liquid of the present invention".

According to the gel-containing pulverized liquid of the present invention, a functional porous body can be formed, for example, by forming a coating film thereof and chemically bonding the pulverized materials in the coating film to each other. According to the gel-containing pulverized material liquid of the present invention, for example, the above-mentioned functional porous body can be imparted to various objects. Specifically, the functional porous body obtained by using the gel-containing pulverized material liquid of the present invention can be used as a heat insulating material, a sound absorbing material, a stent for regenerative medical treatment, a dew-preventing agent, an optical member, etc., for example, instead of an air layer. . Therefore, the gel-containing pulverized material liquid of the present invention and a method for producing the same are useful, for example, in the production of the aforementioned functional porous body.

Since the gel-containing pulverized material system of the present invention has extremely excellent uniformity as described above, for example, when the functional porous body is used for an optical member or the like, the appearance can be improved.

The gel-containing pulverized liquid of the present invention may be, for example, a layer having a high void ratio (high void layer) by coating (coating) the gel-containing pulverized liquid on a substrate and further drying it. A gel-containing pulverized liquid used. Further, the gel-containing pulverized liquid of the present invention may be, for example, a gel-containing pulverized liquid for obtaining a high void ratio porous body (thickness or block-like bulk). The above block system can be obtained, for example, by integrally forming a film using the gel-containing pulverized liquid.

For example, a layer having a high void ratio (high void layer) can be produced by a production method comprising the steps of producing the gel-containing pulverized liquid of the present invention by the above-described method for producing a gel-containing pulverized liquid of the present invention. And a step of applying the gel-containing pulverized liquid to the substrate to form a coating film, and drying the coating film. Hereinafter, such a manufacturing method may be referred to as "the method for producing a high void layer of the present invention". Further, in the following, a high void layer produced by the method for producing a high void layer of the present invention may be referred to as "the high void layer of the present invention". The high void layer of the present invention may be, for example, a high void layer having a void ratio of 60% by volume or more.

Further, for example, a porous body (high void ratio porous body) having a high void ratio can be produced by a production method including the following steps: producing the gelation of the present invention by the above-described method for producing a gel-containing pulverized liquid of the present invention a step of pulverizing the liquid and a step of drying the liquid containing the pulverized material. Hereinafter, such a production method may be referred to as "the method for producing a high void ratio porous body of the present invention". In the following, the high void ratio porous body produced by the method for producing a high void ratio porous body of the present invention may be referred to as "the high void ratio porous body of the present invention". The high void ratio porous body of the present invention may be, for example, a high void ratio porous body having a porosity of 60% by volume or more.

Further, for example, a laminated film web can be produced by a production method including the following steps: a step of producing the gel-containing pulverized liquid of the present invention by the above-described method for producing a gel-containing pulverized liquid of the present invention, and a roll-like method a step of outputting the resin film, a step of coating the gel-containing pulverized material liquid to form a coating film on the output resin film, a step of drying the coating film, and a resin to be dried after the drying step A step of winding a laminated film having the aforementioned high void layer formed on the film. Hereinafter, such a manufacturing method may be referred to as "the method for producing a laminated film web of the present invention". In the following, the high void ratio porous body produced by the method for producing a laminated film roll of the present invention may be referred to as "the laminated film roll of the present invention". In the laminated film roll of the present invention, the high void layer may be, for example, a high void layer having a void ratio of 60% by volume or more.

[1. Gel-containing pulverized liquid and method for producing the same] The gel-containing pulverized liquid system of the present invention includes, for example, a gel pulverized by the pulverization step (for example, the first pulverization stage and the second pulverization stage). The pulverized material, as well as the aforementioned other solvents.

The method for producing a gel-containing pulverized material liquid according to the present invention includes a pulverization step for pulverizing the gel (for example, a porous body gel) in multiple stages, and includes, for example, the first pulverization stage and the second pulverization stage. Hereinafter, the method of producing the gel-containing pulverized liquid of the present invention will be described as an example including the first pulverization stage and the second pulverization stage. Hereinafter, the case where the gel is a porous body (porous body gel) will be mainly described. However, the present invention is not limited thereto, and the above-described gel may be applied to the description of the porous body (porous body gel) in addition to the case where the gel is a porous body. In the following, the plurality of pulverization stages (for example, the first pulverization stage and the second pulverization stage) in the method for producing a gel-containing pulverized material of the present invention may be collectively referred to as a "pulverization step".

The gel-containing pulverized material liquid system of the present invention can be used for producing a functional porous body which exhibits the same function (for example, low refractive index) as the air layer, as will be described later. Specifically, the gel-containing pulverized material liquid obtained by the production method of the present invention contains the pulverized material of the porous body gel, and the three-dimensional structure of the porous body gel which is not pulverized in the pulverized material is destroyed. A new three-dimensional structure different from the above-described pulverized porous body gel can be formed. Therefore, for example, a coating film (functional porous body precursor) formed using the gel-containing pulverized liquid described above may become a layer in which a new pore structure (new void structure) is formed, which is not pulverized by using the foregoing. The layer formed by the porous body gel cannot be obtained. Thereby, the layer can exhibit the same function as the air layer (for example, the same low refractive index). Further, the gel-containing pulverized material of the present invention, after containing a sterol group remaining as the pulverized material, forms a new three-dimensional structure as the coating film (functional precursor of the functional porous body), the pulverized material Chemically bonded to each other. Thereby, although the functional porous body formed is a structure having a void, sufficient strength and flexibility can be maintained. Therefore, the functional porous body can be easily and simply imparted to a wide variety of objects by the present invention. The gel-containing pulverized material liquid obtained by the production method of the present invention is very useful, for example, in the production of the above porous structure which can be used as a substitute for the air layer. Further, in the case of the air layer, for example, by providing a gap between the component and the component via a spacer or the like, it is necessary to form an air layer between the components. However, the above-described functional porous body formed by using the gel-containing pulverized material of the present invention can exhibit the same function as the air layer by merely arranging it in the target portion. Therefore, as described above, it is easier and simpler to impart the same function as the air layer to a wide variety of objects than the formation of the air layer. Specifically, the porous structure can be used as a heat insulating material, a sound absorbing material, a stent for regenerative medical treatment, a dew condensation preventing material, or the like, for example, instead of the air layer.

The gel-containing pulverized liquid system of the present invention can be used, for example, as a solution for forming the functional porous body or a solution for forming a low refractive layer. In the gel-containing pulverized material liquid of the present invention, the porous body is a pulverized material.

In the gel-containing pulverized material liquid of the present invention, the volume average particle diameter of the pulverized material (porous body gel particles) is, for example, 10 to 1000 nm, 100 to 500 nm, or 200 to 300 nm. The volume average particle diameter is a particle size deviation of the pulverized material in the gel-containing pulverized material liquid of the present invention. The volume average particle diameter can be measured by, for example, a particle size distribution analyzer such as a dynamic light scattering method or a laser diffraction method, an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). .

Further, in the gel-containing pulverized material liquid of the present invention, the gel concentration of the pulverized product is not particularly limited, and for example, particles having a particle diameter of 10 to 1000 nm account for 2.5 to 4.5% by weight, 2.7 to 4.0% by weight, and 2.8 to 3.2% by weight. .

In the gel-containing pulverized material liquid of the present invention, the gel (for example, a porous body gel) is not particularly limited, and examples thereof include a hydrazine compound.

The ruthenium compound is not particularly limited, and examples thereof include a ruthenium compound containing at least a trifunctional or less saturated bond functional group. The above "a saturated functional group containing a trifunctional or lower functional group" means that the fluorene compound has three or less functional groups, and these functional groups form a saturated bond with cerium (Si).

The above hydrazine compound is, for example, a compound represented by the following formula (2). [Chemical 1]

In the above formula (2), for example, X is 2, 3 or 4, and R ¹ and R ² are each a linear or branched alkyl group, and R ¹ and R ² may be the same or different, and R ^{1 is} at X. In the case of 2, they may be the same or different from each other, and R ² may be the same or different from each other.

For example, the X and R ¹ are the same lines in the above formula (1) of the X and R ¹ are. Further, the above R ² type can be exemplified, for example, by R ¹ in the following formula (1).

Specific examples of the oxime compound represented by the above formula (2) include a compound represented by the following formula (2') wherein X is 3. In the following formula (2'), R ¹ and R ² are each the same as the above formula (2). When R ¹ and R ² are a methyl group, the above hydrazine compound is trimethoxy(methyl)decane (hereinafter also referred to as "MTMS"). [Chemical 2]

In the gel-containing pulverized liquid of the present invention, the pulverized substance concentration of the aforementioned porous body gel in the above solvent is not particularly limited, and is, for example, 0.3 to 50% (v/v), 0.5 to 30% (v/v). ), 1.0 to 10% (v/v). When the concentration of the pulverized material is too high, for example, the fluidity of the gel-containing pulverized liquid may be remarkably lowered to cause coagulum or smear at the time of coating. On the other hand, when the concentration of the pulverized material is too low, for example, it takes not only a long period of time for drying the solvent, but also a large amount of residual solvent immediately after drying, and there is a possibility that the void ratio is lowered.

The physical properties of the gel-containing pulverized liquid of the present invention are not particularly limited. The shear viscosity of the aforementioned gel-containing pulverized liquid is, for example, at a shear rate of 1000 l/s, for example, 1 mPa ‧ to 1 Pa ‧ s, 1 mPa ‧ to 500 mPa ‧ s, 1 mPa ‧ to 50 mPa ‧ s, 1 mPa ‧ s to 30mPa‧s, 1mPa‧s to 10mPa‧s, 10mPa‧s to 1Pa‧s, 10mPa‧s to 500mPa‧s, 10mPa‧s to 50mPa‧s, 10mPa‧s to 30mPa‧s, 30mPa‧s to 1Pa‧s, 30mPa‧s to 500mPa‧s, 30mPa‧s to 50mPa‧s, 50mPa‧s to 1Pa‧s, 50mPa‧s to 500mPa‧s, or 500mPa‧s to 1Pa‧s. When the shear viscosity is too high, for example, a scratch may occur, and a problem such as a decrease in transfer rate of gravure coating may occur. Conversely, once the shear viscosity is too low, for example, the wet coating thickness at the time of coating cannot be increased and the desired thickness cannot be obtained after drying.

In the gel-containing pulverized material liquid of the present invention, examples of the solvent include a dispersion medium and the like. The dispersion medium (hereinafter also referred to as "solvent for coating") is not particularly limited, and examples thereof include a gelling solvent and a solvent for pulverization which will be described later, and the solvent for pulverization is preferable. The solvent for coating described above contains an organic solvent having a boiling point of 70 ° C or more and less than 180 ° C and a saturated vapor pressure of 20 kPa or less at 15 ° C.

The aforementioned organic solvent may, for example, be carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene, isobutanol, isopropanol, isoamyl alcohol, 1 - pentanol (butyl methoxide), ethanol (alcohol), ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, Xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, n-butyl acetate, n-propyl acetate, n-amyl acetate, cyclohexanol, cyclohexanone , 1,4-dioxane, N,N-dimethylformamide, styrene, tetrachloroethylene, 1,1,1-trichloroethane, toluene, 1-butanol, 2-butanol, Methyl isobutyl ketone, methyl ethyl ketone, methyl cyclohexane, methyl cyclohexanone, methyl-n-butyl ketone, isoamyl alcohol, and the like. Further, the dispersion medium may contain an appropriate amount of a perfluoro-based surfactant or a ruthenium-based surfactant which lowers the surface tension.

The gel-containing pulverized material liquid of the present invention may, for example, be a sol particle liquid, that is, a sol-like pulverized material dispersed in the dispersion medium. The gel-containing pulverized material liquid system of the present invention can be continuously formed into a void layer having a certain level or higher strength by, for example, coating and drying on a substrate, followed by chemical crosslinking by a bonding step to be described later. In addition, the "sol" in the present invention refers to a state in which the pulverized material (particles of the porous body sol which maintains a three-dimensional structure of a partial void structure) is dispersed in a solvent to exhibit fluidity by pulverizing the three-dimensional structure of the gel. .

The gel-containing pulverized material liquid of the present invention may further contain, for example, a catalyst for chemically bonding the pulverized materials of the gels to each other. The content of the aforementioned catalyst is not particularly limited, and is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight based on the weight of the gelled product.

Further, the gel-containing pulverized material liquid of the present invention may further contain, for example, a crosslinking auxiliary agent for indirectly bonding the gel-pulverized materials to each other. The content of the crosslinking auxiliary agent is not particularly limited, and is, for example, 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight based on the weight of the gelled product.

Further, the gel-containing pulverized liquid of the present invention may have a functional group ratio which does not contribute to the intra-gel crosslinked structure in the functional group of the constituent unit monomer of the gel, and may be, for example, 30 mol% or less, 25 mol% or less, or 20 mol%. Hereinafter, it may be 15 mol% or less, and may be, for example, 1 mol% or more, 2 mol% or more, 3 mol% or more, or 4 mol% or more. The functional group ratio which does not contribute to the intra-gel crosslinked structure can be measured, for example, as follows.

(Measurement method of functional group ratio which does not contribute to cross-linking structure in gel) After drying the gel, solid state NMR (Si-NMR) is measured, and residual sterol groups which are not beneficial to the crosslinked structure are calculated from the peak ratio of NMR (no benefit) The ratio of the functional groups of the crosslinked structure in the gel. Further, in the case where the above functional group is other than the decyl group, the ratio of the functional group which does not contribute to the intra-gel crosslinked structure can be calculated from the NMR peak ratio in this manner.

Hereinafter, the production method of the present invention will be described. However, the gel-containing pulverized material liquid of the present invention can be used as follows unless otherwise specified.

In the production method of the present invention, the mixing step may be carried out by mixing the particles (pulverized product) of the porous body gel with the solvent. Specific examples of the mixing step include a step of mixing a pulverized product of a gelatinous ruthenium compound (ruthenium compound gel) with a dispersion medium, and the pulverized product of the ruthenium compound gel is obtained by saturating at least 3 functional groups or less. A bond-functional oxime compound. In the present invention, the pulverized material of the porous body gel can be obtained from the porous body gel by a pulverization step described later. Further, the pulverized material of the porous body gel can be obtained, for example, from the porous body gel after the aging treatment in the aging step described later.

In the production method of the present invention, the gelation step is, for example, a step of gelling a bulk porous body into a porous body gel in a solvent, and a specific example of the gelation step is, for example, at least 3 The step of gelling a compound having a saturated bond functional group below the functional group to form a ruthenium compound gel.

Hereinafter, the gelation step will be described by taking the case where the porous body is a ruthenium compound.

The gelation step is a step of gelatinizing the aforementioned hydrazine compound of the monomer by a dehydration condensation reaction, for example, in the presence of a dehydration condensation catalyst, whereby a hydrazine compound gel is obtained. The ruthenium compound gel has, for example, a residual sterol group, and the residual sterol group is preferably appropriately adjusted in accordance with chemical bonding between the pulverized materials of the bismuth compound gel described later.

In the gelation step, the hydrazine compound is not particularly limited as long as it can be gelated by a dehydration condensation reaction. By the aforementioned dehydration condensation, for example, the aforementioned ruthenium compounds are bonded to each other. The combination between the aforementioned hydrazine compounds is, for example, a hydrogen bond or an intermolecular force bond.

The hydrazine compound may, for example, be an anthracene compound represented by the following formula (1). Since the oxime compound of the above formula (1) has a hydroxyl group, it is possible to form a hydrogen bond or an intermolecular force bond between the ruthenium compounds of the above formula (1), for example, via the respective hydroxyl groups.

[Chemical 3]

In the above formula (1), for example, X is 2, 3 or 4, and R ¹ is a linear or branched alkyl group. The carbon number of the above R ¹ is, for example, 1 to 6, 1 to 4, and 1 to 2. The linear alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. The branched alkyl group may, for example, be an isopropyl group or an isobutyl group. The aforementioned X is, for example, 3 or 4.

Specific examples of the oxime compound represented by the above formula (1) include a compound represented by the following formula (1') wherein X is 3. In the following formula (1'), R ^{1 is the} same as the above formula (1), and is, for example, a methyl group. When R ¹ is a methyl group, the above hydrazine compound is gin (hydroxy)methyl decane. When X is 3, the above hydrazine compound is, for example, a trifunctional decane having three functional groups.

[Chemical 4]

Further, specific examples of the oxime compound represented by the above formula (1) include a compound wherein X is 4. In this case, the above hydrazine compound is, for example, a tetrafunctional decane having four functional groups.

The hydrazine compound may be, for example, a precursor of the hydrazine compound of the above formula (1) by hydrolysis. The precursor may be, for example, a compound which can form the above-mentioned oxime compound by hydrolysis, and a compound represented by the above formula (2) is exemplified as a specific example.

When the hydrazine compound is a precursor represented by the above formula (2), the production method of the present invention may include, for example, a step of hydrolyzing the precursor before the gelation step.

The method of the aforementioned hydrolysis is not particularly limited and can be carried out, for example, by a chemical reaction in the presence of a catalyst. The above catalyst may, for example, be an acid such as oxalic acid or acetic acid. The hydrolysis reaction can be carried out, for example, by slowly dropping an aqueous solution of oxalic acid into a dimethyl hydrazine solution mixed with the ruthenium compound precursor in a room temperature environment, and then stirring the state for about 30 minutes. When the precursor of the ruthenium compound is hydrolyzed, for example, the alkoxy group of the precursor of the ruthenium compound can be completely hydrolyzed to more effectively exhibit subsequent gelation, aging, and heating and immobilization after formation of the void structure.

In the present invention, the above-mentioned hydrazine compound is, for example, a hydrolyzate of trimethoxy(methyl)decane.

The oxime compound of the above monomer is not particularly limited, and can be appropriately selected, for example, depending on the use of the functional porous body to be produced. In the production of the above-mentioned functional porous material, for example, when the low refractive index property is emphasized, the trifunctional decane is preferable from the viewpoint of excellent low refractive index, and the strength is emphasized (for example, In the case of scratch resistance, the above-mentioned tetrafunctional decane is preferred from the viewpoint of scratch resistance. In addition, the above-mentioned hydrazine compound which is the raw material of the cerium compound gel may be used alone or in combination of two or more kinds. In a specific example, the monomer ruthenium compound may contain only the above-mentioned trifunctional decane, or may contain only the above-mentioned tetrafunctional decane, or may contain both the above-mentioned trifunctional decane and the above-mentioned tetrafunctional decane, and may further contain other矽 compound. When two or more kinds of hydrazine compounds are used in the above hydrazine compound, the ratio thereof is not particularly limited and can be appropriately set.

The gelation of the porous body such as the ruthenium compound can be carried out, for example, by a dehydration condensation reaction between the porous bodies. The dehydration condensation reaction is preferably carried out, for example, in the presence of a catalyst, and examples of the catalyst include a dehydration condensation catalyst such as an acid catalyst and a basic catalyst, and the acid catalyst includes hydrochloric acid, oxalic acid, sulfuric acid, etc., and the alkaline catalyst. There are ammonia, potassium hydroxide, sodium hydroxide, ammonium hydroxide and the like. The dehydration condensation catalyst may be an acid catalyst or an alkali catalyst, but a base catalyst is preferred. In the above dehydration condensation reaction, the amount of the catalyst added to the porous body is not particularly limited, and the catalyst is, for example, 0.01 to 10 m, 0.05 to 7 m, 0.1 with respect to the porous body 1 mol. Up to 5 moles.

The gelation of the porous body such as the above ruthenium compound is preferably carried out, for example, in a solvent. The proportion of the aforementioned porous body in the aforementioned solvent is not particularly limited. The aforementioned solvent may, for example, be dimethyl hydrazine (DMSO), N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc), dimethylformamide (DMF), γ- Butyrolactone (GBL), acetonitrile (MeCN), ethylene glycol ethyl ether (EGEE), and the like. The solvent may be used alone or in combination of two or more. The solvent used for the gelation described below is also referred to as "solvent for gelation" hereinafter.

The conditions of the gelation described above are not particularly limited. The treatment temperature for the aforementioned solvent containing the above porous body is, for example, 20 to 30 ° C, 22 to 28 ° C, and 24 to 26 ° C, and the treatment time is, for example, 1 to 60 minutes, 5 to 40 minutes, and 10 to 30 minutes. When the dehydration condensation reaction is carried out, the treatment conditions are not particularly limited, and the examples can be used. When the porous body is a ruthenium compound by the gelation, for example, a siloxane bond is grown, and the primary particles of the ruthenium compound are formed, and further, by the progress of the reaction, the primary particles are linked. It is a beaded shape and produces a three-dimensional structure of the gel.

The gel form of the aforementioned porous body obtained in the aforementioned gelation step is not particularly limited. In general, "gel" refers to a structure in which a solute has an independent kinetic activity due to interaction and is in a solidified state. Further, in the gel, in general, a wet gel refers to a structure containing a dispersion medium and having the same solute in a dispersion medium, and a dry gel means a solvent having a mesh structure in which a solvent is removed and a solute has a void. In the present invention, the aforementioned cerium compound gel is preferably, for example, a wet gel. When the porous body gel is a cerium compound gel, the residual sterol group of the cerium compound gel is not particularly limited, and for example, it can be similarly exemplified as a range described later.

The porous body gel obtained by the gelation may be directly supplied to the solvent replacement step and the first pulverization step, or may be subjected to the aging treatment in the aging step before the first pulverization step. . In the above-mentioned ripening step, the gelled porous body (porous body gel) is aged in a solvent. In the aforementioned ripening step, the conditions of the above-mentioned ripening treatment are not particularly limited, and for example, the porous body gel may be cultured in a solvent at a predetermined temperature. According to the above-described ripening treatment, for example, with respect to the porous body gel having a three-dimensional structure obtained by gelation, the raw particles can be further grown, whereby the size of the particles themselves can be increased. Then, as a result, the neck contact state in which the aforementioned particles are in contact with each other can be increased, for example, from point contact to surface contact. The porous body gel subjected to the above-described aging treatment is, for example, increased in strength, and as a result, the strength of the three-dimensional structure of the pulverized material after pulverization can be further enhanced. Thereby, when the coating film is formed using the gel-containing pulverized liquid of the present invention, for example, in the drying step after coating, the solvent volatilization in the coating film generated in the aforementioned drying step can be suppressed. The pore size of the void structure in which the aforementioned three-dimensional basic structure is deposited is thus shrunk.

The lower limit of the temperature of the ripening treatment is, for example, 30° C. or higher, 35° C. or higher, or 40° C. or higher, and the upper limit thereof is, for example, 80° C. or lower, 75° C. or lower, or 70° C. or lower, and the range thereof is, for example, 30 to 80° C., 35 to 75. °C, 40 to 70 °C. The predetermined time is not particularly limited, and the lower limit thereof is, for example, 5 hours or longer, 10 hours or longer, or 15 hours or longer, and the upper limit thereof is, for example, 50 hours or shorter, 40 hours or shorter, 30 hours or shorter, and the range is, for example, 5 to 50 hours, 10 Up to 40 hours, 15 to 30 hours. Further, as for the most suitable conditions for the ripening, for example, as described above, it is preferable to set the size of the primary particles in the porous body gel and to increase the neck contact area. Further, in the above-mentioned ripening step, the temperature of the above-mentioned ripening treatment is preferably, for example, a method in which the boiling point of the solvent to be used is taken into consideration. In the above-mentioned aging treatment, for example, if the aging temperature is too high, the solvent may be excessively volatilized, and the coating liquid may be concentrated to cause a problem that the pores of the three-dimensional void structure are closed. On the other hand, in the above-mentioned ripening treatment, for example, if the ripening temperature is too low, the effect by the above-mentioned ripening cannot be sufficiently obtained, and the temperature deviation over time in the mass production process is increased, and the possibility of producing a product having inferior quality is obtained. .

For the above-mentioned aging treatment, for example, the same solvent as the gelation step described above can be used. Specifically, it is preferable to directly treat the reactant after the gel treatment (that is, the solvent containing the porous body gel). . In the case where the porous body gel is the above-described cerium compound gel, the residual sterol molar amount contained in the cerium compound gel which is subjected to the aging treatment after gelation is, for example, used for gelation. The molar number of the alkoxy group of the raw material (for example, the above-mentioned hydrazine compound or its precursor) is defined as a ratio of residual sterol groups at 100, and the lower limit thereof is, for example, 50% or more, 40% or more, 30% or more, and the upper limit thereof is, for example, It is 1% or less, 3% or less, 5% or less, and its range is, for example, 1 to 50%, 3 to 40%, and 5 to 30%. For the purpose of increasing the hardness of the aforementioned cerium compound gel, for example, the lower the number of moles of the residual sterol group, the better. When the number of moles of the residual sterol group is too high, for example, when the functional porous body is formed, there is a possibility that the void structure cannot be maintained until the functional porous body is crosslinked before the functional porous body. On the other hand, if the number of moles of the residual sterol group is too low, for example, in the above-described bonding step, the precursor of the functional porous body may not be crosslinked, and it may not be possible to impart sufficient film strength. Further, although the above is an example of a residual sterol group, for example, when the ruthenium compound modified with various reactive functional groups is used as the material of the ruthenium compound gel, the same phenomenon can be applied to each functional group.

The porous body gel obtained by the gelation can be subjected to a solvent replacement step after the ripening step, for example, and then subjected to the pulverization step thereafter. In the solvent replacement step, the solvent is replaced with another solvent.

In the present invention, the pulverizing step is a step of pulverizing the porous body gel as described above. The pulverization may be carried out, for example, on the porous body gel after the gelation step, or may be carried out after the aging of the porous body gel after the aging treatment.

Further, as described above, before the solvent replacement step (for example, after the aging step), a gel form control step of controlling the gel shape and size may be performed. The shape and size of the gel to be controlled by the gel form control step are not particularly limited, for example, as described above. The gel morphology control step can be carried out, for example, by dividing (for example, cutting) the gel into a three-dimensional object (a ternary body) of an appropriate size and shape.

Further, as described above, the pulverization step is carried out after the solvent replacement step is performed on the gel. In the solvent replacement step, the solvent is replaced with another solvent. This is because if the solvent is not replaced with the other solvent, for example, the catalyst and the solvent used in the gelation step may remain after the above-mentioned ripening step, and further gelation may occur over time to affect the final stage. The shelf life of the obtained gel-containing pulverized material liquid may have a possibility that the drying efficiency at the time of drying may be lowered by the coating film formed using the gel-containing pulverized material liquid. Further, the other solvent in the gel grinding step described below is also referred to as "solvent solvent" hereinafter.

The solvent for pulverization (other solvent) is not particularly limited, and for example, an organic solvent can be used. The organic solvent may, for example, be a solvent having a boiling point of 140 ° C or less, 130 ° C or less, a boiling point of 100 ° C or less, and a boiling point of 85 ° C or less. Specific examples thereof include isopropyl alcohol (IPA), ethanol, methanol, n-butanol, 2-butanol, isobutanol, pentanol, propylene glycol monomethyl ether (PGME), acesulfame, acetone, and the like. . The solvent for pulverization may be used alone or in combination of two or more kinds.

Further, in the case where the polarity of the solvent for pulverization is low, for example, the solvent replacement step may be carried out in a plurality of solvent replacement steps, and in the solvent replacement step, it is preferable to perform the subsequent steps. The aforementioned other solvents at the stage are less hydrophilic. By doing so, for example, the solvent replacement efficiency can be improved, and the residual amount of the solvent (for example, DMSO) for gel production in the gel can be made extremely low. As a specific example, for example, the solvent replacement step can be carried out in a three-stage solvent replacement step. First, the DMSO in the gel is replaced with water in the first solvent replacement step, and then the gel is replaced in the second solvent replacement step. The water is replaced by IPA, and the aforementioned IPA in the gel is replaced with isobutanol in the third replacement stage.

The combination of the solvent for gelation and the solvent for pulverization is not particularly limited, and examples thereof include a combination of DMSO and IPA, a combination of DMSO and ethanol, a combination of DMSO and isobutanol, a combination of DMSO and n-butanol, and the like. By replacing the solvent for gelation with the solvent for pulverization, for example, a relatively uniform coating film can be formed in the formation of a coating film to be described later.

The solvent replacement step is not particularly limited, and can be carried out, for example, as follows. That is, first, the gel produced by the gel production step (for example, the gel after the aging treatment) is immersed or brought into contact with the other solvent, and the gel-forming touch in the gel is dissolved in the other solvent. The medium, the alcohol component formed by the condensation reaction, water, and the like. Then, the solvent impregnated or contacted with the aforementioned gel is discarded, and the gel is again immersed or brought into contact with a new solvent. This is repeated until the residual amount of the solvent for gel production in the gel is as high as desired. The immersion time per one time is, for example, 0.5 hours or longer, 1 hour or longer, or 1.5 hours or longer, and the upper limit 値 is not particularly limited to, for example, 10 hours or shorter. Further, the impregnation of the above solvent may correspond to the continuous contact of the solvent with the gel. Further, the temperature during the immersion is not particularly limited, and may be, for example, 20 to 70 ° C, 25 to 65 ° C or 30 to 60 ° C. Once heated, the solvent replacement is accelerated, and the amount of solvent required for replacement is reduced, but solvent replacement can be easily performed at room temperature. Further, for example, when the solvent replacement step is carried out in a plurality of solvent replacement steps, the plurality of solvent replacement steps may be carried out as described above.

Then, after the solvent replacement step, the gel is pulverized in the solvent for pulverization to carry out a gel pulverization step. Further, for example, as described above, after the solvent replacement step, the gel concentration may be measured before the gel pulverization step, and the gel concentration adjustment step may be performed thereafter. The gel concentration measurement before the gel pulverization step after the solvent replacement step can be carried out, for example, in the following manner. That is, first, after the solvent replacement step, the gel is taken out from the other solvent (solvent for pulverization). This gel is a gel block which is controlled to an appropriate shape and size (for example, a block shape) by the gel form control step, for example. Next, the solvent adhering to the periphery of the gel block was removed, and then the solid content concentration of one gel block was measured by a weight drying method. At this time, in order to obtain the reproducibility of the measurement enthalpy, a plurality of (for example, six) gel pieces taken out at random are measured, and the deviation between the average enthalpy and enthalpy is calculated. In the concentration adjustment step, for example, the gel concentration of the liquid containing the gel can be lowered by further adding the other solvent (solvent for pulverization). Further, in the concentration adjustment step, conversely, the gel concentration of the liquid containing the gel can be increased by evaporating the other solvent (solvent for pulverization).

In the method for producing a gel-containing pulverized material liquid of the present invention, as described above, the pulverization step is carried out by dividing the pulverization step into a plurality of pulverization stages, specifically, for example, performing the first pulverization stage and the second pulverization stage. . However, the pulverization step may be further subjected to a pulverization step in addition to the first pulverization stage and the second pulverization stage. That is, in the production method of the present invention, the pulverization step is not limited to the two-stage pulverization step, and may include three or more pulverization stages.

Hereinafter, the first pulverization stage and the second pulverization stage will be described.

The first pulverization step is a step of pulverizing the porous body gel. The second pulverization step is a step of further pulverizing the particles of the porous body gel after the first pulverization step.

The particle volume average particle diameter of the porous body gel obtained through the first pulverization step and the particle volume average particle diameter of the porous body gel obtained through the second pulverization step are as described above. The method for measuring the volume average particle diameter is also as described above.

The shear viscosity of the gel-containing pulverized material liquid immediately after the completion of the first pulverization stage and immediately after the second pulverization stage is as described above. The method for measuring the shear viscosity described above is also as described above.

Further, as described above, the gel concentration of the gel-containing liquid may be measured immediately after the end of the first pulverization step, and only the liquid having the gel concentration within a predetermined number 値 may be supplied to the second pulverization stage. Thereby, the concentration management of the liquid containing the aforementioned gel is performed.

The pulverization method of the porous body gel is not particularly limited, and for example, a high-pressure medium-free pulverizing apparatus, an ultrasonic homogenizer, a high-speed rotary homogenizer, a high-pressure extrusion pulverizing apparatus, and a wet type medium pulverizing apparatus using other cavitation phenomena. Wait. The same pulverization method may be carried out in the first pulverization stage and the second pulverization stage, and different pulverization methods may be carried out, but it is preferred to carry out pulverization methods different from each other.

As the pulverization method, at least one of the first pulverization stage and the second pulverization stage is preferably carried out by a method of pulverizing the porous body gel by controlling energy. The method of pulverizing the porous body gel by controlling energy is, for example, a method performed by a high-pressure medium-free pulverizing apparatus or the like.

The method of pulverizing the porous body gel by ultrasonication has a strong pulverization strength, but it is difficult to control (monitor) the degree of pulverization. On the other hand, if the porous body gel is pulverized by controlling energy, it is possible to control (monitor) the pulverization while performing pulverization. Thereby, a uniform gel-containing pulverized liquid can be produced in a limited amount of work. Therefore, the gel-containing pulverized material liquid can be produced, for example, on a mass production basis.

For example, a device for pulverizing a medium such as a ball mill that physically destroys a gel structure during pulverization, and a cavitation pulverizing device such as a homogenizer can be wrapped in a three-dimensional structure of a gel, for example, by using a medium-free method. The porous particle-joining surface, which is relatively weak in binding force, is peeled off at a high shear stress. Thus, by pulverizing the porous body gel, a new three-dimensional structure of the sol is obtained, and the three-dimensional structure can maintain a void structure having a certain range of particle size distribution, for example, by coating and drying. The resulting void structure. The pulverization conditions are not particularly limited. For example, it is preferred to pulverize the gel so as not to volatilize the solvent by instantaneously imparting a high-speed flow. For example, it is preferred to carry out pulverization so as to be a pulverized material having a particle size deviation (for example, a volume average particle diameter or a particle size distribution) as described above. When the amount of work such as the pulverization time and the strength is insufficient, for example, there are residual coarse particles, it is impossible to form dense pores, and appearance defects are increased, and high quality cannot be obtained. On the other hand, when the amount of work is too large, for example, sol particles which are finer than the desired particle size distribution may be formed, and the void size which is deposited after drying by coating may be made fine, and a desired void ratio may not be obtained.

It is preferable to control the pulverization of the porous body while measuring the shear viscosity of the liquid in at least one of the first pulverization stage and the second pulverization stage. Specific examples include, for example, a method of adjusting a sol liquid having both a desired shear viscosity and an extremely good uniformity in the middle of the pulverization stage, and monitoring the shear viscosity of the liquid in-line and feeding back to the foregoing. The method of the crushing stage. Thereby, a gel-containing pulverized liquid having both the desired shear viscosity and excellent uniformity can be produced. Therefore, for example, the characteristics of the aforementioned gel-containing pulverized liquid can be controlled depending on the use thereof.

When the porous body gel is the cerium compound gel after the pulverization step, the ratio of the residual sterol groups contained in the pulverized material is not particularly limited, and for example, it may be related to the cerium compound gel after the aging treatment. The scope of the illustration is the same.

In the production method of the present invention, the classification step may be further performed after at least one of the pulverization step (the first pulverization stage and the second pulverization stage). The above classification step is to classify the particles of the aforementioned porous body gel. The above-mentioned "classification" means, for example, an operation of distinguishing the particles of the porous body gel by the particle diameter. The method of classification is not particularly limited and can be carried out using a sieve. By performing the pulverization treatment in a plurality of stages as described above, the uniformity is extremely excellent as described above. Therefore, when it is used for an optical member or the like, the appearance thereof can be improved, and the appearance can be changed by further performing classification treatment. Better.

After the pulverization step and the arranging step, the ratio of the pulverized material in the solvent containing the pulverized material is not particularly limited, and examples thereof include the conditions of the above-described gel-containing pulverized material of the present invention. The ratio may be, for example, a condition in which the solvent itself of the ground product is contained after the pulverization step, or may be a condition adjusted before the pulverization step is used as the gel-containing pulverized liquid.

As described above, a liquid (for example, a suspension) containing the fine pore particles (pulverized product of the gelled compound) can be produced. Further, after the liquid containing the fine pore particles is produced or during the production process, a catalyst containing the fine pore particles and the catalyst can be prepared by adding a catalyst which chemically bonds the fine pore particles to each other. . The amount of the catalyst to be added is not particularly limited, and may be, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight based on the weight of the pulverized product of the gelled cerium compound. The catalyst may be, for example, a catalyst that promotes cross-linking of the aforementioned fine pore particles to each other. The chemical reaction for chemically bonding the aforementioned fine pore particles to each other is preferably carried out by a dehydration condensation reaction of a residual stanol group contained in the cerium oxide sol molecule. By the above-mentioned catalyst, the reaction between the hydroxyl groups of the stanol groups can be promoted, and the continuous film formation in which the void structure is hardened in a short time can be achieved. The aforementioned catalyst may be, for example, a photoactive catalyst and a thermally active catalyst. According to the above photoactive catalyst, for example, in the above-described void layer forming step, the fine pore particles can be chemically bonded (for example, crosslinked) to each other without heating. Thereby, for example, in the void layer forming step, shrinkage of the entire void layer is not easily caused by heating, so that a high void ratio can be maintained. Further, in addition to the above-mentioned catalyst, a substance capable of generating a catalyst (catalyst generating agent) may be used or replaced. For example, in addition to the photoactive catalyst described above, a substance (photocatalyst generator) which generates a catalyst by light may be used or replaced; or a substance which generates a catalyst by heat may be used in addition to the above-mentioned thermally active catalyst. (hot catalyst generator) or replace it. The photocatalyst generating agent is not particularly limited, and examples thereof include a photobase generator (a substance which generates an alkaline catalyst by irradiation), a photoacid generator (a substance which generates an acid catalyst by irradiation), and the like. The generator is preferred. The aforementioned photobase generator may be, for example, 9-anthrylmethyl N, N-diethylcarbamate (trade name: WPBG-018), (E)-1-[ 3-(2-hydroxyphenyl)-2-propenyl] piperidine ((E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine, trade name WPBG-027), 1-( 2-(anthraquinon-2-yl)ethyl imidazolecarboxylate (trade name: WPBG-140), 2-nitrophenylmethyl 4-methylpropenyloxypiperidine 1-carboxylic acid ester (trade name: WPBG-165), 1,2-diisopropyl-3-[bis(dimethylamino)methylene]fluorene 2-(3-benzhydrylphenyl)propene Acid ester (trade name: WPBG-266), 1,2-dicyclohexyl-4,4,5,5-tetramethylbis-n-butyltriphenyl borate (trade name: WPBG-300) and 2- (9-oxadibenzopipene-2-yl)propionic acid 1,5,7-triazabicyclo[4.4.0]non-5-ene (Tokyo Chemical Industry Co., Ltd.), containing 4-piperidyl A compound of pyridine methanol (trade name: HDPD-PB100: manufactured by Heraeus Co., Ltd.) or the like. In addition, the trade names containing "WPBG" mentioned above are the trade names of Wako Pure Chemical Industries Co., Ltd. The photoacid generator may, for example, be an aromatic onium salt (trade name: SP-170: ADEKA), a triarylsulfonium salt (trade name: CPI101A: San-Apro Ltd.), or an aromatic onium salt (trade name: Irgacure 250: Ciba Japan) KK) and so on. Further, the catalyst for chemically bonding the fine pore particles to each other is not limited by the photoactive catalyst and the photocatalyst generating agent, and may be, for example, a thermally active catalyst or a thermal catalyst generating agent. The catalyst for chemically bonding the fine pore particles to each other may be an alkaline catalyst such as potassium hydroxide, sodium hydroxide or ammonium hydroxide, or an acid catalyst such as hydrochloric acid, acetic acid or oxalic acid. Among them, alkaline catalyst is preferred. The catalyst or catalyst generating agent that chemically bonds the fine pore particles to each other can be added, for example, to a sol particle liquid (for example, a suspension) containing the pulverized material (fine pore particles) before being coated. The method is used, or is used by mixing the aforementioned catalyst or catalyst generating agent into a mixture of solvents. The mixed liquid is, for example, a coating liquid which is directly added to the sol particle liquid and dissolved, a solution in which the catalyst or the catalyst generating agent is dissolved in a solvent, or a catalyst or a catalyst generating agent may be dispersed in the solvent. A dispersion of the solvent. The solvent is not particularly limited, and examples thereof include water, a buffer solution and the like.

[2. Method of using gel-containing pulverized liquid] The method for using the gel-containing pulverized liquid of the present invention is exemplified below by the method for producing a porous porphyrite porous body, but the present invention does not Limited by this.

The method for producing a porous polysiloxane porous body, characterized in that, for example, the gel-containing pulverized material liquid of the present invention is used, and a precursor forming step of forming the precursor of the porous polysiloxane porous body and a precursor forming step are used. The bonding step of chemically bonding the aforementioned pulverized materials containing the gel-pulverized liquid to each other. The aforementioned precursor may also be referred to as a coating film, for example.

According to the method for producing a porous polysiloxane body, for example, a porous structure exhibiting the same function as the air layer is formed. The reason for this can be estimated, for example, as follows, but the present invention is not limited by this.

In the gel-containing pulverized liquid of the present invention used in the method for producing a porous polysiloxane, the three-dimensional structure of the gel-like cerium oxide compound is obtained by containing the pulverized material of the cerium compound gel. It is dispersed in the state of the three-dimensional basic structure. Therefore, in the method for producing a porous polysiloxane body, for example, the precursor (for example, a coating film) is formed using the gel-containing pulverized material liquid, and the three-dimensional basic structure is deposited to form a void structure based on the three-dimensional basic structure. That is, according to the method for producing a porous polysiloxane, a new three-dimensional structure formed from the pulverized material of the three-dimensional basic structure, which is different from the three-dimensional structure of the cerium compound gel, is formed. Further, in the method for producing a porous polysiloxane body, since the pulverized materials are further chemically bonded to each other, the new three-dimensional structure is fixed. Therefore, the porous polysiloxane porous body obtained by the method for producing a porous polysiloxane porous body has a structure having a void, but can maintain sufficient strength and flexibility. The polyaluminum oxide porous body obtained by the present invention can be used as a component using a void, for example, in a wide range of fields such as a heat insulating material, a sound absorbing material, an optical member, and an ink absorbing layer, and further, various functions can be produced. Laminated film.

The method for producing the porous polysiloxane porous body can be referred to the description of the gel-containing pulverized material liquid of the present invention unless otherwise specified.

In the step of forming the porous body precursor, for example, the gel-containing pulverized material of the present invention described above is applied onto the substrate. The gel-containing pulverized liquid system of the present invention is applied, for example, by coating on a substrate, and after the coating film is dried, the pulverized materials are chemically bonded (for example, crosslinked) to each other through the above-described bonding step. The void layer having a certain level or higher strength can be continuously formed.

The amount of the gel-containing pulverized liquid to be applied to the substrate is not particularly limited, and may be appropriately set, for example, according to the thickness of the porous polysiloxane body or the like. In a specific example, when the porous polysiloxane porous body having a thickness of 0.1 to 1000 μm is formed, the coating amount of the gel-containing pulverized liquid to the substrate is 1 m ² per unit area, for example, 0.01% of the pulverized material. Up to 60,000 μg, 0.1 to 5000 μg, and 1 to 50 μg. The desired coating amount of the gel-containing pulverized liquid described above is related to, for example, the liquid concentration or the coating method, and thus it is difficult to generalize, and in view of productivity, it is preferable to coat as much as possible in a thin layer. When the amount of coating is too large, for example, the possibility of drying in a drying oven before the solvent is volatilized increases. As a result, before the nanosized pulverized sol particles are deposited in a solvent and deposited to form a void structure, the formation of the voids may be hindered by drying of the solvent, and the void ratio may be greatly lowered. On the other hand, when the coating amount is too small, the risk of coating shrinkage may increase due to unevenness of the substrate, variation in hydrophobicity, and the like.

After the gel-containing pulverized material liquid is applied to the base material, the precursor (coating film) of the porous body described above may be subjected to a drying treatment. By the drying treatment, for example, not only the solvent (the solvent contained in the gel-containing pulverized liquid) in the porous body precursor can be removed, but also the sol particles are sedimented and deposited in the drying process. A void structure is formed. The temperature of the drying treatment is, for example, 50 to 250 ° C, 60 to 150 ° C, and 70 to 130 ° C, and the drying treatment time is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, or 0.3 to 3 minutes. Regarding the drying treatment temperature and time, for example, in terms of continuous productivity or exhibiting a high void ratio, it is preferably a lower temperature and a shorter time. If the conditions are excessively severe, for example, in the case where the substrate is a resin film, the substrate may be stretched in a drying oven due to the glass transition temperature of the substrate, and may be formed in the void immediately after coating. The structure has defects such as cracks. On the other hand, if the condition is too loose, the residual solvent may be contained at, for example, the time of leaving the drying furnace, so that a scratch or the like occurs when rubbing against the roller member in the next step, and an appearance defect occurs.

The drying treatment may be, for example, natural drying, heat drying, or drying under reduced pressure. The aforementioned drying method is not particularly limited, and for example, a general heating mechanism can be used. The heating means may be, for example, a hot air blower, a heat roller, a far infrared heater or the like. Among them, under the premise of continuous production in the industry, it is preferred to use heat drying. Further, in the solvent which can be used, when the purpose is to suppress the shrinkage stress caused by the volatilization of the solvent during drying and the subsequent cracking of the void layer (the porous polysiloxane), the solvent having a low surface tension is good. The solvent may, for example, be a lower alcohol represented by isopropyl alcohol (IPA), hexane, perfluorohexane or the like, but is not limited thereto.

The substrate is not particularly limited, and a substrate made of a thermoplastic resin, a substrate made of glass, an inorganic substrate typified by ruthenium, a plastic or a semiconductor formed by a thermosetting resin, or the like can be suitably used. The carbon fiber-based material represented by the carbon nanotube is, but is not limited to. Examples of the form of the substrate include a film, a plate, and the like. Examples of the thermoplastic resin include polyethylene terephthalate (PET), acrylic resin, cellulose acetate propionate (CAP), cycloolefin polymer (COP), triacetate (TAC), and polynaphthalene. Ethylene dicarboxylate (PEN), polyethylene (PE), polypropylene (PP), and the like.

In the method for producing a porous polysiloxane body, the bonding step is a step of chemically bonding the pulverized materials contained in the porous body precursor (coating film) to each other. For example, by the aforementioned bonding step, the three-dimensional structure of the pulverized material in the precursor of the porous body is fixed. When immobilization is carried out by conventional sintering, the dehydration condensation of a stanol group is excited by, for example, performing a high temperature treatment at 200 ° C or higher to form a siloxane coupling. In the above-mentioned bonding step of the present invention, for example, when the substrate is a resin film, by reacting various additives capable of catalyzing the above-described dehydration condensation reaction, it is possible to reduce the temperature to about 100 ° C without damaging the substrate. The low drying temperature and the short processing time of less than several minutes continuously form and fix the void structure.

The method of chemically bonding the above is not particularly limited, and can be appropriately determined depending on, for example, the type of the above-mentioned cerium compound gel. In a specific example, the chemical bonding system can be carried out, for example, by chemically crosslinking the pulverized materials, and it is also conceivable that, for example, when inorganic particles such as titanium oxide are added to the pulverized material, the inorganic particles are added. A method of chemically crosslinking the pulverized material. Further, in the case of providing a biocatalyst such as an enzyme, it is also possible to chemically crosslink the site different from the catalytic activity point to the pulverized material. Therefore, the present invention is not limited to, for example, a void layer (polyaluminum oxide porous body) formed of the above-described sol particles, and is conceivable to be applied to an organic-inorganic hybrid void layer, a host-guest void layer, or the like, but is not limited thereto.

The above-described bonding step can be carried out, for example, by a chemical reaction in the presence of a catalyst in accordance with the kind of the pulverized material of the cerium compound gel. In the chemical reaction in the present invention, it is preferred to use a dehydration condensation reaction of a residual sterol group contained in the pulverized material of the above-mentioned cerium compound gel. By the above-mentioned catalyst, the reaction between the hydroxyl groups of the stanol groups can be promoted, and the continuous film formation in which the void structure is hardened in a short time can be achieved. The catalyst may, for example, be an alkaline catalyst such as potassium hydroxide, sodium hydroxide or ammonium hydroxide, or an acid catalyst such as hydrochloric acid, acetic acid or oxalic acid, but is not limited thereto. The catalyst for the dehydration condensation reaction described above is preferably a basic catalyst. Further, a photoacid generating catalyst or a photobase generating catalyst or the like which exhibits catalytic activity by irradiation can be suitably used. The photoacid generating catalyst and the photobase generating catalyst are not particularly limited, but are as described above, for example. For example, as described above, the catalyst is preferably added to the sol particle liquid containing the pulverized material before being applied, or preferably used as a mixed liquid in which the catalyst is mixed in a solvent. The mixed liquid may be, for example, a coating liquid dissolved in the sol particle liquid, a solution in which the catalyst is dissolved in a solvent, or a dispersion in which the catalyst is dispersed in a solvent. The solvent is not particularly limited, and examples thereof include water, a buffer, and the like.

Further, for example, in the gel-containing liquid of the present invention, a crosslinking auxiliary agent for indirectly bonding the pulverized materials of the gel may be further added. The crosslinking auxiliary agent enters between the particles (the aforementioned pulverized material), and the particles and the crosslinking auxiliary agent interact or combine with each other, so that particles farther apart can be combined with each other, and the strength can be efficiently increased. The crosslinking assistant is preferably a multi-crosslinked decane monomer. The multi-crosslinked decane monomer specifically has, for example, an alkoxyfluorenyl group of 2 or more and 3 or less, and a chain length between the alkoxy fluorenyl groups may be 1 or more and 10 or less carbon atoms, and may contain an element other than carbon. The crosslinking assistant may, for example, be bis(trimethoxyindenyl)ethane, bis(triethoxyindenyl)ethane, bis(trimethoxyindenyl)methane, bis(triethoxyindenyl)methane or double (triethoxyindolyl)propane, bis(trimethoxyindolyl)propane, bis(triethoxyindenyl)butane, bis(trimethoxyindenyl)butane, bis(triethoxyindenyl)pentane, Bis(trimethoxyindolyl)pentane, bis(triethoxyindenyl)hexane, bis(trimethoxyindolyl)hexane, bis(trimethoxyindolyl)-N-butyl-N-propyl-B Alkane-1,2-diamine, gins(3-trimethoxydecylpropyl)trimeric isocyanate, ginseng (3-triethoxydecylpropyl)trimeric isocyanate, and the like. The amount of the crosslinking auxiliary agent to be added is not particularly limited, and is, for example, 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight based on the weight of the aforementioned cerium compound pulverized product.

The chemical reaction in the presence of a catalyst can be carried out, for example, by the fact that the catalyst or catalyst generator has been previously added to the gel-containing pulverized liquid, and the catalyst or catalyst is contained. The coating film of the agent is irradiated or heated; or the above-mentioned coating film is sprayed with the above-mentioned catalyst or catalyst generating agent, and then irradiated or heated; or light is sprayed while spraying the above-mentioned catalyst or catalyst generating agent. Irradiation or heating. For example, when the catalyst is a photoactive catalyst, the microporous particles can be chemically bonded to each other by irradiation to form the porous polysiloxane. Further, when the catalyst is a thermally active catalyst, the microporous particles may be chemically bonded to each other by heating to form the polysiloxane porous body. The amount of illumination (energy) of the aforementioned illumination is not particularly limited, but may be, for example, 200 to 800 mJ/cm ² , 250 to 600 mJ/cm ² , and 300 to 400 mJ/cm ² in terms of @360 nm. When the amount of irradiation is insufficient, the decomposition effect of light absorption by the catalyst generating agent is stagnant and the effect is not good, and from the viewpoint of avoiding the above, the amount of integrated light of 200 mJ/cm ² or more is preferable. Further, from the viewpoint of avoiding damage to the substrate under the void layer and causing thermal wrinkles, the cumulative amount of light of 800 mJ/cm ² or less is preferable. The wavelength of light at the time of the illumination is not particularly limited, and is, for example, 200 to 500 nm or 300 to 450 nm. The light irradiation time at the time of the illumination is not particularly limited, and is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, and 0.3 to 3 minutes. The conditions of the heat treatment are not particularly limited, and the heating temperature is, for example, 50 to 250 ° C, 60 to 150 ° C, and 70 to 130 ° C, and the heating time is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, or 0.3 to 3 minutes. Further, in terms of a solvent which can be used, for example, when the purpose is to suppress shrinkage stress caused by volatilization of the solvent during drying, and the subsequent cracking of the void layer, a solvent having a low surface tension is preferred. For example, a lower alcohol represented by isopropyl alcohol (IPA), hexane, perfluorohexane or the like may be mentioned, but is not limited thereto.

A polysiloxane porous body can be produced by the above method. Further, the porous polysiloxane porous body produced in this manner is hereinafter also referred to as "the porous polysiloxane porous body of the present invention". However, the method for producing the porous polysiloxane porous body of the present invention is not limited to the above. Further, the porous polysiloxane body of the present invention may be, for example, one of the high void layer of the present invention or the high void ratio porous body of the present invention.

Further, for example, the obtained polyaluminum oxide porous body of the present invention may be subjected to a strength upgrading step by heat treatment or the like to increase the strength (hereinafter also referred to as "curing step"). For example, in the case where the polysiloxane porous body of the present invention is laminated on the resin film, the adhesion peeling strength with respect to the resin film can be improved by the strength increasing step (aging step). In the aforementioned strength increasing step (aging step), for example, the porous polysiloxane porous body of the present invention can be heated. The temperature of the ripening step is, for example, 40 to 80 ° C, 50 to 70 ° C, and 55 to 65 ° C. The reaction time is, for example, 5 to 30 hr, 7 to 25 hr, or 10 to 20 hr. In the above-mentioned aging step, for example, by setting the heating temperature to a low temperature, the peeling adhesion strength can be improved while suppressing the shrinkage of the porous polysiloxane porous body, and both the high void ratio and the strength can be achieved.

Although the phenomenon and mechanism occurring in the strength increasing step (aging step) are not known, it is conceivable that the microporous particles are further chemically bonded to each other by the catalyst contained in the porous polysiloxane porous body of the present invention. (eg cross-linking reaction) to increase strength. In a specific example, when the residual sterol group (OH group) is present in the porous polysiloxane porous body, it is conceivable that the residual sterol groups are chemically bonded to each other via a crosslinking reaction. Further, the catalyst contained in the porous polysiloxane porous body of the present invention is not particularly limited, and may be, for example, a catalyst used in the above-described bonding step, or may be a photobase generating catalyst used in the above-described bonding step. The alkaline substance generated by the light or the photoacid used in the above-mentioned bonding step generates an acidic substance generated by the irradiation of the catalyst. However, the description is for illustrative purposes and does not limit the invention.

Further, an adhesive layer (adhesive layer formation step) may be further formed on the polysiloxane porous body of the present invention. Specifically, for example, an adhesive or an adhesive may be applied to the porous polysiloxane porous body of the present invention, whereby the adhesive layer may be formed. Further, an adhesive tape or the like having the above-mentioned adhesive layer laminated on the substrate can be attached to the porous polysiloxane porous body of the present invention, whereby the polysiloxane porous body of the present invention can be laminated. The aforementioned adhesive layer is formed. At this time, the base material of the adhesive tape or the like can be kept in a bonded state, and can be peeled off from the adhesive layer. In the present invention, the "adhesive" and "adhesive layer" mean, for example, an agent or layer which is premised on the re-peelability of the adherend. In the present invention, the "adhesive agent" and the "adhesive layer" mean, for example, an agent or a layer which is not required to be re-peelable by the adherend. However, in the present invention, the "adhesive" and the "adhesive" are not necessarily clearly distinguishable, and the "adhesive layer" and the "adhesive layer" are not necessarily clearly distinguishable. In the present invention, the adhesive or the adhesive for forming the adhesive layer is not particularly limited, and for example, a general adhesive or an adhesive can be used. Examples of the pressure-sensitive adhesive or the adhesive include a polymer-based adhesive such as an acrylic, a vinyl alcohol, a polyoxymethylene, a polyester, a polyurethane, or a polyether; and a rubber-based adhesive. Further, an adhesive agent composed of a water-soluble crosslinking agent such as a vinyl alcohol polymer such as glutaraldehyde, melamine or oxalic acid may be used. These adhesives and adhesives may be used alone or in combination (for example, mixed, laminated, etc.). The thickness of the adhesive layer is not particularly limited and is, for example, 0.1 to 100 μm, 5 to 50 μm, 10 to 30 μm, or 12 to 25 μm.

Further, the porous polysiloxane porous body of the present invention may be reacted with the adhesive layer to form an intermediate layer disposed between the polysiloxane porous body of the present invention and the adhesive layer (intermediate layer forming step). By the intermediate layer, for example, the porous polysiloxane porous body of the present invention and the adhesive layer are hardly peeled off. The reason (mechanism) is unknown, and it is presumed that it is due to the anchoring property (the anchoring effect) of the aforementioned intermediate layer. The anchoring property (anchoring effect) refers to a phenomenon in which the intermediate layer is formed in the vicinity of the interface between the void layer and the intermediate layer, and the intermediate layer is embedded in the inside of the void layer, so that the interface is firmly fixed. However, the reason (mechanism) is only an example of the reason (mechanism) of speculation, and the present invention cannot be limited. The reaction of the porous polysiloxane porous body of the present invention and the above-mentioned adhesive layer is not particularly limited, and for example, it may be a reaction by a catalyst. The catalyst may be, for example, a catalyst contained in the porous polysiloxane body of the present invention. Specifically, for example, it may be the catalyst used in the above-mentioned bonding step, or may be the alkaline substance generated by the photobase generating catalyst used in the above-mentioned bonding step, or may be the light used in the aforementioned bonding step. The acid generates an acidic substance or the like which is generated by the catalyst through illumination. Further, the reaction of the porous polysiloxane porous body of the present invention with the above-mentioned adhesive layer may be, for example, a reaction for producing a new chemical bond (for example, a crosslinking reaction). The temperature of the above reaction is, for example, 40 to 80 ° C, 50 to 70 ° C, and 55 to 65 ° C. The reaction time is, for example, 5 to 30 hr, 7 to 25 hr, or 10 to 20 hr. Further, the intermediate layer forming step may be carried out in combination with the aforementioned strength increasing step (aging step) for enhancing the strength of the polyoxynitride porous body of the present invention.

The porous polysiloxane body of the present invention obtained in this manner may be laminated with another film (layer) to form a laminated structure including the porous structure. In this case, in the laminated structure, each constituent element may be laminated, for example, via an adhesive or an adhesive.

The layer of each of the above-described constituent elements can be laminated by, for example, continuous processing using a long film (so-called roll-to-roll), etc., depending on the efficiency, and when the substrate is a molded article/element or the like, After batch processing, laminate it.

Hereinafter, a method of forming the above-mentioned polyfluorinated porous body on a substrate using the above-described gel-containing pulverized liquid of the present invention will be exemplified using FIGS. 1 to 3. 2 is a view showing a step of laminating a protective film and winding it after the porous polysiloxane body is formed, and the above method may be used for laminating another functional film, or another functional film may be applied. After drying, the above-mentioned film-forming porous polysiloxane body is bonded before the film is being wound up. In addition, the film formation method shown in the figure is only an example, and is not limited to this.

In the cross-sectional view of Fig. 1, an example of a step in the method of forming the porous polysiloxane porous body on the substrate is schematically shown. In Fig. 1, the method for forming a porous polysiloxane porous body comprises: a coating step (1) of applying the gel-containing pulverized liquid 20'' of the present invention to a substrate 10; a coating film forming step (drying step) (2), drying the gel-containing pulverized liquid 20'' to form a coating film 20' which is the foregoing precursor layer of the polysiloxane porous body; and a chemical treatment step ( For example, in the crosslinking treatment step (3), the coating film 20' is subjected to a chemical treatment (for example, a crosslinking treatment) to form a polysiloxane porous body 20. In this way, the polysiloxane porous body 20 can be formed on the substrate 10 as shown. Further, the method for forming the porous polysiloxane porous body may or may not include the steps other than the above steps (1) to (3).

In the coating step (1), the coating method of the gel-containing pulverized liquid 20'' is not particularly limited, and a general coating method can be employed. The coating method may be, for example, a slot die method, a reverse gravure coat method, a micro gravure method (micro gravure coat method), or the like. Dipping method (dip coating method), spin coating method, brush coating method, roll coating method, flexographic printing method, wire bar coating method, spray coating method, extrusion coating method, curtain coating method, reverse Coating method, etc. Among these, it is preferable to use an extrusion coating method, a curtain coating method, a roll coating method, a micro gravure coating method, or the like from the viewpoints of productivity, smoothness of a coating film, and the like. The coating amount of the gel-containing pulverized liquid 20'' is not particularly limited, and can be appropriately set, for example, such that the porous structure (polyphosphorus porous body) 20 has an appropriate thickness. The thickness of the porous structure (polysiloxane porous body) 20 is not particularly limited and may be as described above.

In the drying step (2), the gel-containing pulverized liquid 20'' is dried (i.e., the dispersion medium contained in the gel-containing pulverized liquid 20'' is removed) to form a coating film (precursor layer) 20'. The conditions of the drying treatment are not particularly limited as described above.

Further, in the chemical treatment step (3), coating the above-mentioned catalyst (for example, a photoactive catalyst, a photocatalyst generating agent, a thermal active catalyst or a thermal catalyst generating agent) which has been added before the coating is applied. The film 20' is irradiated or heated to chemically bond (e.g., crosslink) the pulverized materials in the coating film (precursor) 20' to each other to form a polysiloxane porous body 20. The illumination or heating conditions of the chemical treatment step (3) are not particularly limited as described above.

Next, Fig. 2 is a view schematically showing an example of a slit die coating apparatus and a method of forming the above-mentioned polysiloxane porous body using the apparatus. In addition, although FIG. 2 is a cross-sectional view, hatching is omitted for ease of reading.

As shown, each step of the method of using the apparatus performs this step by transporting the substrate 10 in one direction while the roller member. The conveying speed is not particularly limited, and is, for example, 1 to 100 m/min, 3 to 50 m/min, and 5 to 30 m/min.

First, the substrate 10 is output from the delivery roller 101 for transport, and the coating step (1) is applied to the coating roller 102, that is, the gel-containing pulverized liquid 20'' of the present invention is applied onto the substrate, and then continued. Transition to the drying step (2) in the oven zone 110. In the coating apparatus of Fig. 2, the pre-drying step is carried out before the drying step (2) after the coating step (1). The pre-drying step can be carried out at room temperature without heating. The heating mechanism 111 is used in the drying step (2). As described above, the heating mechanism 111 can suitably use a hot air heater, a heating roller, a far infrared heater or the like. Further, for example, the drying step (2) can be divided into a plurality of steps such that the drying temperature becomes higher as the subsequent drying step becomes higher.

After the drying step (2), the chemical treatment step (3) is carried out in the chemical treatment zone 120. In the chemical treatment step (3), for example, when the coated film 20' after drying contains a photoactive catalyst, it is irradiated with a lamp (illuminating means) 121 disposed above and below the substrate 10. Alternatively, for example, when the coated film 20' after drying contains a thermally active catalyst, a hot air blower (heating means) is used instead of the lamp (illuminating means) 121, and the substrate 10 is heated by the air heater 121 disposed above and below the substrate 10. . By the crosslinking treatment, the pulverized materials in the coating film 20' are chemically bonded to each other, and the polysiloxane porous body 20 is hardened and strengthened. Then, after the chemical treatment step (3), the layered body of the porous polysiloxane porous body 20 is wound on the substrate 10 by the winding roller 105. Further, in Fig. 2, the porous structure 20 of the above laminated body is coated and protected by a protective sheet output from the roller member 106. Here, another layer formed of a long film may be laminated on the porous structure 20 instead of the protective sheet.

Fig. 3 schematically shows a coating apparatus of a micro gravure method (microgravure coating method) and an example of the above-described porous structure forming method using the same. In addition, although this figure is a sectional view, hatching is abbreviate|omitted for readability.

As shown in the figure, each step of the method using the apparatus is carried out in the same manner as in Fig. 2 by conveying the substrate 10 in one direction by the roller member. The conveying speed is not particularly limited, and is, for example, 1 to 100 m/min, 3 to 50 m/min, and 5 to 30 m/min.

First, the coating step (1) is carried out while the substrate 10 is outputted from the delivery roller 201, and the gel-containing pulverized liquid 20'' of the present invention is applied to the substrate 10. The coating of the gel-containing pulverized liquid 20'' is carried out by means of a liquid storage zone 202, a doctor knife 203 and a micro gravure 204 as shown. Specifically, the gel-containing pulverized liquid 20'' stored in the liquid storage area 202 is attached to the surface of the micro-gravure 204, and then controlled to a predetermined thickness by the doctor blade 203 while being coated on the substrate with the micro-gravure 204. 10 surface. Further, the micro gravure 204 is exemplified, and is not limited thereto, and any other coating mechanism may be used.

Next, the drying step (2) is carried out. Specifically, the substrate 10 coated with the gel-containing pulverized liquid 20'' is conveyed to the oven section 210 as shown, and dried by heating by the heating means 211 in the oven section 210. The heating mechanism 211 can also be the same as that of FIG. 2, for example. Further, for example, the drying step (2) can be divided into a plurality of steps by dividing the oven zone 210 into a plurality of blocks, so that the drying temperature becomes higher and higher with the subsequent drying step. After the drying step (2), the chemical treatment step (3) is carried out in the chemical treatment zone 220. In the chemical treatment step (3), for example, when the coated film 20' after drying contains a photoactive catalyst, it is irradiated with a lamp (illumination mechanism) 221 disposed above and below the substrate 10. Alternatively, for example, when the dried coating film 20' contains a thermally active catalyst, a hot air heater (heating mechanism) is used instead of the lamp (illuminating device) 221 to arrange the air heater (heating mechanism) under the substrate 10. The substrate 10 is heated 221 . By the crosslinking treatment, the pulverized materials in the coating film 20' are chemically bonded to each other to form the polysiloxane porous body 20.

Then, after the chemical treatment step (3), the laminate of the porous polysiloxane porous body 20 is wound on the substrate 10 by the take-up roll 251. Thereafter, for example, another layer may be laminated on the laminate. Further, before the laminated body is wound by the take-up roll 251, the other layers of the laminated volume layer may be formed.

In addition, Figs. 4 to 6 show another example of the continuous processing steps in the method for forming a polysiloxane porous body of the present invention. As shown in the cross-sectional view of Fig. 4, in addition to the strength upgrading step (aging step) (4) after the chemical treatment step (e.g., cross-linking treatment) (3) of forming the poly-oxygen porous body 20, The methods shown in Figures 1 to 3 are the same. As shown in Fig. 4, the strength increasing step (aging step) (4) enhances the strength of the porous polysiloxane porous body 20 to form a porous polysiloxane porous body 21 having an increased strength. The strength increasing step (aging step) (4) is not particularly limited, and is as described above.

Fig. 5 is a schematic view showing another example of a coating apparatus of a slit type die coating method different from that of Fig. 2 and a method of forming the above-mentioned polyfluorinated porous body using the apparatus. As shown in the figure, the coating apparatus is followed by the chemical treatment zone 120 of the chemical treatment step (3), followed by a strength enhancement zone (maturing zone) 130 for performing the strength upgrading step (aging step) (4), in addition to The same as the device of Figure 2. That is, after the chemical treatment step (3), a strength-increasing step (aging step) (4) is performed in the strength-enhancing region (curing zone) 130 to increase the peeling adhesion strength of the polysilicon porous body 20 to the resin film 10, A polysiloxane porous body 21 having an improved peeling adhesion strength is formed. The strength increasing step (aging step) (4) can be carried out, for example, by heating the polysiloxane porous body 20 by using a hot air heater (heating means) 131 disposed on the upper and lower sides of the substrate 10. The heating temperature, time, and the like are not particularly limited, and are as described above. Thereafter, a laminated film in which the porous polysiloxane porous body 21 is formed on the substrate 10 is taken up by the take-up roll 105 in the same manner as in FIG.

Fig. 6 is a schematic view showing another example of a micro gravure method (microgravure coating method) coating apparatus different from Fig. 3 and a method of forming the above porous structure using the apparatus. As shown in the figure, the coating apparatus is followed by the chemical treatment zone 220 of the chemical treatment step (3), followed by a strength enhancement zone (maturing zone) 230 for performing the strength upgrading step (aging step) (4), in addition to The same as the device of FIG. That is, after the chemical treatment step (3), a strength-increasing step (aging step) (4) is performed in the strength-enhancing region (maturing region) 230 to increase the peeling adhesion strength of the polysiloxane porous body 20 to the resin film 10, A polysiloxane porous body 21 having an improved peeling adhesion strength is formed. The strength increasing step (aging step) (4) can be carried out, for example, by using a hot air heater (heating means) 231 disposed on the upper and lower sides of the substrate 10, as described above, to heat the polysiloxane porous body 20. The heating temperature, time, and the like are not particularly limited, and are as described above. Thereafter, a laminated film in which the porous polysiloxane porous body 21 is formed on the substrate 10 is wound by the take-up roll 251 in the same manner as in FIG.

Further, Figs. 7 to 9 show another example of the continuous processing steps in the method for forming a porous porous oxygen body of the present invention. As shown in the cross-sectional view of FIG. 7, after the chemical treatment step (for example, the crosslinking treatment step) (3) of forming the polysiloxane porous body 20, the method comprises: an adhesive layer coating step (adhesion layer formation step) (4), which is applied to the porous oxyporous body 20 with the adhesive layer 30; and an intermediate layer forming step (5) for reacting the porous siloxane porous body 20 with the adhesive layer 30 to form the intermediate layer 22. Except for these, the methods of FIGS. 7 to 9 are the same as those shown in FIGS. 4 to 6. Further, in Fig. 7, the intermediate layer forming step (5) serves as a step of increasing the strength of the polysiloxane porous body 20 (strength enhancing step), and after the intermediate layer forming step (5), the polysiloxane porous body 20 is changed. It is a polysiloxane porous body 21 having an increased strength. However, the present invention is not limited thereto, and for example, the polysiloxane porous body 20 may not change after the intermediate layer forming step (5). The adhesive adhesion layer coating step (adhesive layer formation step) (4) and the intermediate layer formation step (5) are not particularly limited, and are as described above.

Fig. 8 is a schematic view showing still another example of the coating apparatus of the slit die coating method and the method of forming the above-mentioned polyoxynitride porous body using the apparatus. As shown, the coating apparatus is followed by the chemical treatment zone 120 of the chemical treatment step (3), followed by the adhesive layer coating zone 130a for performing the adhesive layer coating step (4), in addition to the drawings. The device of 5 is the same. In the figure, the intermediate layer forming region (curing zone) 130 disposed immediately behind the adhesive layer coating region 130a can be improved by the heat exchanger (heating mechanism) 131 disposed above and below the substrate 10, and the strength of FIG. The zone (maturing zone) 130 is subjected to the same heat treatment. That is, in the apparatus of Fig. 8, after the chemical treatment step (3), an adhesive layer coating step (adhesive layer formation step) (4) is performed, that is, by adhering in the adhesive layer coating region 130a. The layer coating mechanism 131a coats (coats) an adhesive or an adhesive on the polysiloxane porous body 20 to form an adhesive layer 30. Further, as described above, the bonding (adhesion) of the adhesive tape or the like having the adhesive layer 30 may be used instead of the application (coating) of the adhesive or the adhesive. Further, an intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming region (aging region) 130, and the polysiloxane porous body 20 is reacted with the adhesive layer 30 to form the intermediate layer 22. Further, as described above, in this step, the polysiloxane porous body 20 becomes a polysiloxane porous body 21 having an increased strength. The heating temperature, time, and the like by the air heater (heating means) 131 are not particularly limited, and are, for example, as described above.

Fig. 9 is a schematic view showing still another example of a coating apparatus of a micro gravure method (microgravure coating method) and a method of forming the above porous structure using the apparatus. As shown, the coating apparatus is followed by the chemical treatment zone 220 of the chemical treatment step (3), followed by the adhesive layer coating zone 230a for performing the adhesive layer coating step (4), in addition to the drawings. The device of 6 is the same. In the figure, the intermediate layer forming region (curing zone) 230 disposed immediately behind the adhesive layer coating region 230a can be improved by the heat exchanger (heating mechanism) 231 disposed above and below the substrate 10, and the strength of FIG. The zone (maturing zone) 230 is subjected to the same heat treatment. That is, in the apparatus of Fig. 9, after the chemical treatment step (3), an adhesive layer coating step (adhesive layer formation step) (4) is performed, that is, by adhering in the adhesive layer coating region 230a. The layer coating mechanism 231a coats (coats) an adhesive or an adhesive on the polysiloxane porous body 20 to form an adhesive layer 30. Further, as described above, the bonding (adhesion) of the adhesive tape or the like having the adhesive layer 30 may be used instead of the application (coating) of the adhesive or the adhesive. Further, an intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming region (aging region) 230, and the polysiloxane porous body 20 is reacted with the adhesive layer 30 to form the intermediate layer 22. Further, as described above, in this step, the polysiloxane porous body 20 becomes a polysiloxane porous body 21 having an increased strength. The heating temperature, time, and the like by the air heater (heating means) 231 are not particularly limited, and are, for example, as described above.

[3. Functionally capable porous body] The functional porous system of the present invention can be, for example, 60% to 100% of the scratch resistance measured by BEMCOT (registered trademark), and is obtained from the MIT test indicating flexibility. The number of folding resistance is 100 or more, but is not limited to this.

In the functional porous body of the present invention, for example, since the pulverized material of the porous body gel is used, the three-dimensional structure of the porous body gel is broken, and a new three-dimensional structure different from the porous body gel is formed. Thus, the functional porous body of the present invention is a layer formed of a new pore structure (new void structure), and the layer formed of the aforementioned porous body gel is not obtained from the structure, whereby a nanometer having a high void ratio can be formed. Grade functional porous body. Further, in the case of the functional porous body of the present invention, for example, in the case where the functional porous body is a polysiloxane porous body, for example, the pulverization of the oxime compound gel is performed while adjusting the number of oxirane bond functional groups. The materials are chemically bonded to each other. Further, since the new three-dimensional structure of the precursor of the functional porous body is formed and chemically bonded (for example, crosslinked) in the bonding step, the functional porous body of the present invention is functional, for example, in the aforementioned functional porous body. Although the porous body has a structure having a void, it can maintain sufficient strength and flexibility. Therefore, according to the present invention, the functional porous body can be easily and easily applied to various objects. Specifically, the functional porous body of the present invention can be used as a heat insulating material, a sound absorbing material, a stent for regenerative medical treatment, a dew condensation preventing material, an optical member, or the like, for example, instead of the air layer.

The functional porous body of the present invention is, for example, a pulverized material containing a porous body gel as described above, and the pulverized materials are chemically bonded to each other. In the functional porous body of the present invention, the chemical bonding form of the pulverized materials is not particularly limited, and specific examples of the chemical bonding include, for example, crosslinking. Further, a method of chemically bonding the pulverized materials to each other will be described in detail in the method for producing the functional porous body described later.

The aforementioned crosslinked bonding system is, for example, a decane bond. The aforementioned oxane bond may be a T2 bond, a T3 bond or a T4 bond as shown below. When the polysiloxane porous body of the present invention has a decane bond, for example, it may have any type of bond, or may have any two types of bonds, or may have all three types of bonds. Among the above-mentioned decane bonds, the more the ratio of T2 and T3, the more flexible and flexible, the more the original properties of the gel are expected, but the strength is weakened. On the other hand, when the ratio of T4 in the above-mentioned decane bond is higher, the film strength is likely to be expressed, but the void size is small and the flexibility is weak. Therefore, the T2, T3, and T4 ratios should be varied depending on, for example, the use.

[Chemical 5]

When the functional porous body of the present invention has the above-described decane bond, the ratio of T2, T3, and T4 is expressed by, for example, T2 being "1", and T2: T3: T4 = 1: [1 - 100 ]: [0 to 50], 1: [1 to 80]: [1 to 40], 1: [5 to 60]: [1 to 30].

Further, the functional porous body of the present invention, for example, preferably contains a ruthenium atom in the form of a ruthenium oxide bond. As a specific example, the ratio of unbonded ruthenium atoms (that is, residual decyl alcohol) among all the ruthenium atoms contained in the porous polysiloxane porous body is, for example, less than 50%, 30% or less, and 15% or less.

The functional porous system of the present invention has a pore structure, and the void size of the pores means the long axis diameter of the void (hole) and the aforementioned long axis diameter in the minor axis diameter. The pore diameter is, for example, 5 nm to 200 nm. The lower limit of the void size is, for example, 5 nm or more, 10 nm or more, or 20 nm or more, and the upper limit thereof is, for example, 1000 μm or less, 500 μm or less, or 100 μm or less, and the range thereof is, for example, 5 nm to 1000 μm, 10 nm to 500 μm, or 20 nm to 100 μm. The void size is determined by the use of the void structure to determine the desired void size. For example, it must be adjusted to the desired void size for the purpose. The void size can be evaluated, for example, by the following method.

(Evaluation of void size) In the present invention, the aforementioned void size can be quantified by the BET test method. Specifically, 0.1 g of a sample (the functional porous body of the present invention) of a specific surface area measuring device (manufactured by Micromeritics Co., Ltd.: ASAP2020) was subjected to vacuum drying at room temperature for 24 hours to form a gas in the void structure. Degas. Nitrogen gas was then adsorbed onto the aforementioned sample, and an adsorption isotherm was drawn to obtain a pore distribution. Thereby the void size can be evaluated.

The functional porous body of the present invention has, for example, a scratch resistance of 60 to 100% as measured by BEMCOT (registered trademark). For example, the present invention is excellent in scratch resistance under various processes because of such strength. The present invention has scratch resistance in the production process after the winding of the functional porous film, for example, and in the production process when the film is processed. On the other hand, the functional porous body of the present invention can increase the particle size of the pulverized material of the cerium compound gel by using a catalyst reaction in a heating step described later, for example, without lowering the void ratio, and the pulverized material of the pulverized material Combines the bonding strength of the neck. Thereby, the functional porous body of the present invention can impart a certain level of strength to the originally fragile void structure, for example.

The lower limit of the scratch resistance is, for example, 60% or more, 80% or more, or 90% or more, and the upper limit thereof is, for example, 100% or less, 99% or less, or 98% or less, and the range is, for example, 60 to 100%, 80 to 99%, 90~98%.

The aforementioned scratch resistance can be measured, for example, by the following method.

(Evaluation of Scratch Resistance) (1) The void layer (the functional porous body of the present invention) which has been coated and formed into an acrylic film is sampled in a circular shape of about 15 mm. (2) Next, the sample was identified by X-ray fluorescence (ZSX Primus II, manufactured by Shimadzu Corporation), and the Si coating amount (Si ₀ ) was measured. Then, the void layer on the acrylic film was cut into 50 mm × 100 mm in the vicinity of the sampling portion and fixed to a glass plate (thickness: 3 mm), and then subjected to a sliding test by Bemcot (registered trademark). . The sliding condition was 100 g by weight and 10 times back and forth. (3) In the same manner as in the above (1), the gap layer was sampled and the fluorescence X measurement was performed, and the Si residual amount (Si1) after the scratch test was measured. The scratch resistance is defined by the residual rate (%) of the 前后 前后 before and after the sliding test of Bemcot (registered trademark), and is expressed by the following formula. Scratch resistance (%) = [residual Si amount (Si ₁ ) / Si coating amount (Si ₀ )] × 100 (%)

The polyfluorinated porous body of the present invention has a folding endurance of 100 or more, for example, as measured by the MIT test. The present invention has excellent operability, for example, due to such flexibility, and thus, for example, during winding up or use of a manufacturing process.

The lower limit of the number of times of folding resistance is, for example, 100 times or more, 500 times or more, or 1,000 times or more, and the upper limit thereof is not particularly limited, and is, for example, 10,000 or less, and the range is, for example, 100 to 10,000 times, 500 to 10,000 times, and 1000 to 10,000 times. .

The aforementioned flexibility means, for example, the ease with which the substance is deformed. The number of folding end points obtained by the MIT test described above can be measured, for example, by the following method.

(Evaluation of the Folding Test) The void layer (the functional porous body of the present invention) was cut into a strip shape of 20 mm × 80 mm, and then placed in an MIT folding tester (BE-202, manufactured by Tester Sangyo Co., Ltd.). 1.0N load. The nip portion for clamping the gap layer was R2.0 mm, the folding end number was 10,000 times at the most, and the number of times when the gap layer was broken was taken as the folding end number.

In the functional porous body of the present invention, the film density at which the void ratio is exhibited is not particularly limited, and the lower limit thereof is, for example, 1 g/cm ³ or more, 5 g/cm ³ or more, 10 g/cm ³ or more, 15 g/cm ³ or more, and the upper limit thereof. For example, it is 50 g/cm ³ or less, 40 g/cm ³ or less, 30 g/cm ³ or less, 2.1 g/cm ³ or less, and the range is, for example, 5 to 50 g/cm ³ , 10 to 40 g/cm ³ , and 15 to 30 g/cm. ³ , 1 to 2.1 g/cm ³ .

The film density can be measured, for example, by the method described below.

(Film Density Evaluation) After forming a void layer (functional porous body of the present invention) on an acrylic film, the X-ray reflectance of the total reflection range was measured using an X-ray diffraction apparatus (RINT-2000, manufactured by RIGAKU Co., Ltd.). After fitting the strength to 2θ, the porosity (P%) was calculated from the critical angle of total reflection of the void layer and the substrate. The film density can be expressed by the following formula. Film density (%) = 100 (%) - void ratio (P%)

The functional porous system of the present invention may have a pore structure (porous structure) as described above, and the pore structure may be, for example, a continuous continuous foam structure. The blister structure, for example, means that the pore structures are connected in three dimensions in the functional porous body; and the internal voids of the pore structure may be connected together. In the case where the porous body has a continuous foam structure, the void ratio occupied by the whole can be increased, but when a single-foamed particle such as hollow ceria is used, a continuous foam structure cannot be formed. On the other hand, in the functional porous body of the present invention, since the sol particles (the pulverized material of the porous body gel forming the sol) have a three-dimensional tree structure, the dendritic particles can be coated on the coating film (including the aforementioned The sedimentation in the coating film of the sol of the porous body gel pulverized material is piled up, and the vesicle structure is easily formed. Further, in the functional porous body of the present invention, it is preferable to form a monolith structure in which the "foamed structure has a plurality of pore distributions". The above monolithic structure refers to, for example, a structure in which nano-sized fine voids are present, and a hierarchical structure in which the same nanovoids are aggregated into a continuous foaming structure. In the case where the monolithic structure is formed, for example, the film strength can be imparted by the fine voids, and the high void ratio can be imparted by the coarse continuous voids, thereby achieving both film strength and high void ratio. To form such a monolithic structure, for example, it is important to first control the pore distribution of the void structure formed by the porous body gel before the pulverization into the pulverized material. Further, for example, when the porous body gel is pulverized, the particle size distribution of the pulverized material can be controlled to a desired size to form the monolithic structure.

In the functional porous body of the present invention, the elongation at break of the fracture which indicates flexibility is not particularly limited, and the lower limit thereof is, for example, 0.1% or more, 0.5% or more, or 1% or more, and the upper limit thereof is, for example, 3% or less. The range of elongation at break of the aforementioned fracture crack is, for example, 0.1 to 3%, 0.5 to 3%, and 1 to 3%.

The elongation at break of the fracture crack can be measured, for example, by the following method.

(Evaluation of elongation at break cracking) After forming a void layer (functional porous body of the present invention) on an acrylic film, sampling was carried out in a strip shape of 5 mm × 140 mm. Then, the sample was sandwiched between tensile tests (manufactured by Shimadzu Corporation: AG-Xplus) so that the distance between the nips was 100 mm, and the tensile test was performed at a tensile speed of 0.1 mm/s. The sample in the test was carefully observed, and when the crack occurred in a part of the sample, the test was terminated, and the elongation (%) at the time of occurrence of the crack was taken as the fracture crack elongation.

In the functional porous body of the present invention, the haze indicating transparency is not particularly limited, and the lower limit thereof is, for example, 0.1% or more, 0.2% or more, or 0.3% or more, and the upper limit thereof is, for example, 10% or less, 5% or less, or 3%. Hereinafter, the range is, for example, 0.1 to 10%, 0.2 to 5%, and 0.3 to 3%.

The haze can be measured, for example, by the following method.

(Evaluation of the haze) The void layer (the functional porous body of the present invention) was cut into a size of 50 mm × 50 mm, and was set to a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.: HM-150) to measure the mist. degree. The haze value is calculated by the following formula. Haze (%) = [Diffuse penetration rate (%) / total light transmittance (%)] × 100 (%)

The refractive index is generally referred to as the ratio of the transmission speed of the light wave surface in the vacuum to the propagation speed in the medium, and is referred to as the refractive index of the medium. The refractive index of the porous polysiloxane porous body of the present invention is not particularly limited, and the upper limit thereof is, for example, 1.3 or less, less than 1.3, 1.25 or less, 1.2 or less, and 1.15 or less, and the lower limit thereof is, for example, 1.05 or more, 1.06 or more, or 1.07 or more. For example, it is 1.05 or more and 1.3 or less, 1.05 or more, less than 1.3, 1.05 or more, 1.25 or less, 1.06 or more, less than 1.2, and 1.07 or more and 1.15 or less.

In the present invention, the refractive index refers to a refractive index measured at a wavelength of 550 nm unless otherwise specified. Further, the method of measuring the refractive index is not particularly limited, and for example, it can be measured by the following method.

(Evaluation of Refractive Index) After forming a void layer (functional porous body of the present invention) on an acrylic film, it was cut into a size of 50 mm × 50 mm, and bonded to the surface of a glass plate (thickness: 3 mm) with an adhesive layer. . The center portion of the back surface of the glass plate (about 20 mm in diameter) was blackened with a black singular pen to prepare a sample which was not reflected on the back surface of the glass plate. The sample was attached to an ellipsometer (manufactured by J. A. Woollam Japan Co., Ltd.: VASE), and the refractive index was measured under the conditions of a wavelength of 500 nm and an incident angle of 50 to 80 degrees, and the average enthalpy was taken as the refractive index.

The thickness of the functional porous body of the present invention is not particularly limited, and the lower limit thereof is, for example, 0.05 μm or more and 0.1 μm or more, and the upper limit thereof is, for example, 1000 μm or less and 100 μm or less, and the range thereof is, for example, 0.05 to 1000 μm and 0.1 to 100 μm.

The form of the functional porous body of the present invention is not particularly limited, and may be, for example, a film form or a block shape.

The method for producing the functional porous body of the present invention is not particularly limited, and can be produced, for example, by the method for producing the above-described functional porous body described below.

[4. Use of the functional porous body] The functional porous system produced by using the gel-containing pulverized material liquid of the present invention has the same function as the air layer as described above, and therefore, for the object having the air layer, It can be used to replace the aforementioned air layer.

Examples of the member including the functional porous body include a heat insulating material, a sound absorbing material, a dew condensation preventing material, and an optical member. These parts can be used, for example, by being placed in a place where an air layer is required. The form of these parts is not particularly limited and may be, for example, a film.

Further, the member including the functional porous body may be, for example, a stent for regenerative medical treatment. The functional porous body as described above has a porous structure that exhibits the same function as the air layer. The pores of the functional porous body are suitable for, for example, a cell, a nutrient source, air, or the like, and the porous structure is useful as a stent for regenerative medicine.

Examples of the component including the functional porous body include a total reflection component, an ink absorbing material, a single layer AR (anti-reflection), a single-layer moth eye, and a dielectric constant material. Example

Next, an embodiment of the present invention will be described. However, the invention is not limited by the following examples.

[Example 1] First, gelation of a ruthenium compound (the following step (1)) and a aging step (step (2) below) were carried out to produce a gel having a porous structure (polysiloxane porous body). . The procedure of the present reference example corresponds to the aforementioned "gel manufacturing step" in the method for producing a gel-containing pulverized liquid of the present invention. However, in the present invention, the aforementioned ripening step can be carried out as described above. Further, the following (3) morphology control step, (4) solvent replacement step, (5) concentration measurement (concentration management) and concentration adjustment step, and (6) pulverization step are carried out to obtain a gel-containing pulverized material liquid. Further, in the present embodiment, as described below, the following (3) mode control step is performed as a step different from the following step (1). However, the present invention is not limited thereto, and the following (3) mode control step may be performed, for example, in the following step (1).

(1) Gelation of hydrazine compound 9.5 kg of hydrazine compound precursor MTMS was dissolved in 22 kg of DMSO. To the mixed liquid, 5 kg of a 0.01 mol/L aqueous oxalic acid solution was added, and MTMS was hydrolyzed by stirring at room temperature for 120 minutes to form hydroxy(hydroxy)methylnonane.

After adding 3.8 kg of 28% aqueous ammonia and 2 kg of pure water to 55 kg of DMSO, the mixed solution subjected to the hydrolysis treatment was further added thereto, and the mixture was stirred at room temperature for 60 minutes. The liquid after stirring for 60 minutes was poured into a stainless steel container having a length of 30 cm, a width of 30 cm, and a height of 5 cm, and allowed to stand at room temperature, whereby gelation of gin (hydroxy)methyldecane was carried out to obtain a gelatinous quinone compound.

(2) Maturation step The gelatinous quinone compound obtained by the gelation treatment was incubated at 40 ° C for 20 hours to carry out a aging treatment to obtain a block-shaped gel having the above-described rectangular parallelepiped shape. In the gel, since DMSO (a high boiling point solvent having a boiling point of 130 ° C or higher) is used in an amount of about 83% by weight based on the entire raw material, it is apparent that it contains 50% by weight or more of a high boiling point solvent having a boiling point of 130 ° C or higher. Further, in the gel, since MTMS (a monomer as a gel constituent unit) in the raw material is used in an amount of about 8% by weight based on the entire raw material, the monomer (MTMS) which is a gel constituent unit is lower than that produced by hydrolysis. The solvent having a boiling point of 130 ° C (in this case, methanol) is apparently contained in an amount of 20% by weight or less.

(3) Morphology control step Isobutanol as a replacement solvent was poured onto the gel synthesized in the above-mentioned 30 cm × 30 cm × 5 cm stainless steel container through the above steps (1) and (2). Next, the cutting blade of the cutting jig was slowly inserted into the gel from above in the stainless steel container, and the gel was cut into a rectangular parallelepiped having a size of 1.5 cm × 2 cm × 5 cm.

(4) Solvent replacement step Further, the cut gel was transferred to another container, and the shape of the gel was not disintegrated, and isobutanol was added in a volume ratio of four times the gel, and left to stand for 6 hours. The solvent was subjected to solvent replacement four times.

(5) Concentration measurement (concentration management) and concentration adjustment step After the solvent replacement step of the above (3), the block-shaped gel is taken out to remove the solvent adhering to the gel. Then, the solid content concentration of the single gel block was measured by a weight drying method. At this time, in order to obtain the reproducibility of the measurement enthalpy, the measurement was performed on the six blocks taken out at random, and the average enthalpy and the number 値 deviation were calculated. At this time, the average enthalpy of the solid content concentration (gel concentration) in the gel was 5.20% by weight, and the deviation of the aforementioned gel concentration 値 in the six gels was within ±0.1%. The measurement enthalpy was adjusted by adding an isobutanol solvent so that the original gel solid content concentration (gel concentration) became about 3.0% by weight.

(6) Pulverization step The gel (gelatinous ruthenium compound) after the concentration measurement (concentration management) and the concentration adjustment step in the above (4) is pulverized in two stages, and the first pulverization stage is continuous emulsification dispersion (Pacific The Miller Company's system, Milder MDN304 type), the second crushing stage is high-pressure medium-free pulverization (Sugino Machine company: Star Burst HJP-25005 type). In the pulverization treatment, 23.4 kg of a gel of a gelatinous bismuth compound containing a solvent was added to the gel, and 26.6 kg of isobutanol was weighed, and then pulverized in a first pulverization step by a cycle pulverization for 20 minutes. 2 The pulverization stage was carried out at a pulverization pressure of 100 MPa. In this manner, an isobutanol dispersion (containing a gel pulverized liquid) in which nanosized particles (the aforementioned gel pulverized product) were dispersed was obtained.

Further, after the first pulverization stage (rough pulverization step) and before the second pulverization stage (nano pulverization step), the solid content concentration (gel concentration) of the liquid (high viscosity gel pulverization liquid) is measured. The result was 3.01% by weight. After the first pulverization stage (rough pulverization step) and before the second pulverization stage (nano pulverization step), the volume average particle diameter of the gel pulverized product is 3 to 5 μm, and the shear viscosity of the liquid is 4,000mPa∙s. Since the high-viscosity gel pulverizing liquid at this time does not have a solid-liquid separation due to high viscosity and can be used as a uniform liquid, the measurement enthalpy after the first pulverization stage (rough pulverization step) is directly used. Further, after the second pulverization stage (nano pulverization step), the volume average particle diameter of the pulverized product of the gel is 250 to 350 nm, and the shear viscosity of the liquid is 5 m to 10 mPa s. Furthermore, after the second pulverization stage (nano pulverization step), the solid content concentration (gel concentration) of the liquid (containing gel pulverized material liquid) was measured again, and it was 3.01% by weight, and the first pulverization was performed. There was no change after the stage (rough pulverization step).

Further, in the present embodiment, the average particle diameter of the pulverized material (sol particles) of the gel after the first pulverization stage and after the second pulverization stage is a dynamic light scattering type Nanotrac particle size analyzer (Japanese machine tool) Company system, product name UPA-EX150 type) identification. Further, in the present embodiment, the shear viscosity of the liquid after the first pulverization stage and after the second pulverization stage is identified by a vibration type viscosity measuring machine (trade name: FEM-1000V, manufactured by Sekonic Corporation). The following examples and comparative examples are also the same.

Further, after the first pulverization step (rough pulverization step), the solid component (gel) of the gel-containing pulverized material liquid is measured (calculated) in the functional group (sterol group) of the constituent unit monomer. The ratio of the functional group (residual sterol group) of the crosslinked structure in the gel gave 11 mol% of the measured enthalpy. Further, the ratio of the functional group (residual sterol group) which does not contribute to the intra-gel crosslinked structure is determined by the following method: after the gel is dried, solid state NMR (Si-NMR) is measured, and it is not advantageous to calculate from the NMR peak ratio. The ratio of residual sterol groups of the crosslinked structure.

[Example 2] The above-mentioned (3) form control step described in Example 1 and the gel synthesis step (gelation of a ruthenium compound) of the above (1) were simultaneously carried out. The mixed solution described in the embodiment (1) was poured into a stainless steel container having a rectangular body length of 2 cm × 3 cm × 5 cm in height, and (1) gelation and (2) aging step were carried out to obtain the block of the rectangular parallelepiped shape. Gel. The block gel is removed from the compartments of the container without being cut, and is directly supplied to the subsequent (4) solvent replacement step. A gel-containing pulverized liquid was produced in the same manner as in Example 1 except the above.

[Comparative Example 1] The concentration adjustment step (5) was carried out after the solvent replacement step (4) described in Example 1, and the concentration (solid concentration) of the solid content in the gel was 5.20% by weight. The first pulverization stage (rough pulverization step) is directly performed. As a result, in the first pulverization stage (rough pulverization step), the liquid excessively formed a high viscosity and the pulverization was incomplete, and it was visually confirmed that there was a gel block having a size of 5 mm or more. In order to further adjust the concentration, the solvent was added after the first pulverization step (rough pulverization step), and as a result, solid-liquid separation was initiated, and it was not possible to use a uniform liquid and the concentration was not measured.

[Comparative Example 2] In the above (5) concentration measurement (concentration management) and concentration adjustment step described in Example 1, the concentration (gel concentration) of the gel solid content was adjusted to about 1.0% by weight, instead of the above-mentioned Example 1. 3.0% by weight. Then, in the same manner as in Example 1, the first pulverization stage (rough pulverization step) and the second pulverization stage (nano pulverization step) in the pulverization step (6) were carried out to obtain a gel-containing pulverized liquid. . In the second pulverization stage (nano pulverization step), the concentration of the gel-containing pulverized liquid is adjusted by the purpose of increasing the thickness of the coating film of the high-void layer by vacuum degassing and heating to remove the solvent. As a result, it was confirmed that particles were aggregated, and it was confirmed that there was precipitation of particulate solids in the liquid after the second pulverization stage (nano pulverization step).

The results of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 are shown in Table 1 below. As shown in the following Table 1, in Examples 1 and 2, after the solvent replacement step and before the start of the first pulverization step, the concentration adjustment (concentration adjustment step) of the liquid containing the gel was performed, and in the initial pulverization stage ( The concentration adjustment of the liquid containing the gel is not performed after the start of the first pulverization stage), and the uniformity of the gel-containing pulverized liquid obtained in the second pulverization stage (nano pulverization step) of the examples. Extremely excellent. On the other hand, in Comparative Example 1, the concentration of the liquid containing the gel was not appropriately adjusted. As described above, the liquid excessively formed a high viscosity and the pulverization was incomplete, and the gel concentration was not measured. Further, in Comparative Example 2, the concentration UP (concentration adjustment) of the gel-containing pulverized material liquid is carried out after the second pulverization stage (nano pulverization step), as described above, in the second pulverization stage (nano pulverization step) After the precipitation of the particulate solids in the liquid, a uniform gel-containing pulverized liquid is not obtained.

[Table 1] Industrial availability

As described above, according to the method for producing a gel-containing pulverized liquid provided by the present invention, even in the mass production of industrial specifications, a gel-containing pulverized liquid having excellent uniformity and high void structure can be produced. When the gel-containing pulverized liquid of the present invention is used, for example, the porous structure can be immobilized by chemically bonding the pulverized materials to each other, and thus the obtained porous structure can maintain the structure having a void. Full strength. Therefore, the porous structure can easily and easily impart a functional porous body to various objects. Specifically, the porous structure can be industrially usable in a wide range of fields such as a heat insulating material, a sound absorbing material, a stent for regenerative medical materials, a dew condensation preventing material, and an optical member, in place of the air layer.

10‧‧‧Substrate
20‧‧‧Porous structure
20'‧‧‧ coated film (precursor layer)
20''‧‧‧gel-containing pulverized liquid
21‧‧‧Strengthened porous structure
101‧‧‧Send rolls
102‧‧‧Application roller
110‧‧‧Oven area
111‧‧‧Hot air heater (heating mechanism)
120‧‧‧Chemical treatment area
121‧‧‧Light (illumination mechanism) or air heater (heating mechanism)
130a‧‧‧Adhesive coating area
130‧‧‧Strength enhancement zone, intermediate zone formation zone
131a‧‧‧Adhesive layer coating mechanism
131‧‧‧Hot air heater (heating mechanism)
105‧‧‧Winding roller
106‧‧‧Roll parts
201‧‧‧Send rolls
202‧‧‧Liquid storage area
203‧‧‧Doctor knife
204‧‧‧ microgravure
210‧‧‧Oven area
211‧‧‧ heating mechanism
220‧‧‧Chemical treatment area
221‧‧‧lights (illumination mechanism) or air heaters (heating mechanism)
230a‧‧‧Adhesive coating area
230‧‧‧Strength enhancement zone, intermediate zone formation zone
231a‧‧‧Adhesive layer coating mechanism
231‧‧‧Hot air heater (heating mechanism)
251‧‧‧Winding roller

Fig. 1 is a cross-sectional view showing an example of a method of forming a functional porous body 20 on a substrate 10 using the gel-containing pulverized liquid of the present invention. Fig. 2 is a view schematically showing a part of the steps of producing a functional porous body using the gel-containing pulverized liquid of the present invention and an apparatus used therefor. Fig. 3 is a view schematically showing a part of the steps of producing a functional porous body using the gel-containing pulverized liquid of the present invention and another example of the apparatus used therein. Figure 4 is a cross-sectional view showing another example of a method of forming a functional porous body on a substrate of the present invention. Fig. 5 is a view schematically showing a part of the steps of producing a functional porous body using the gel-containing pulverized liquid of the present invention and another example of the apparatus used therein. Fig. 6 is a view schematically showing a part of the steps of producing a functional porous body using the gel-containing pulverized liquid of the present invention and another example of the apparatus used therein. Fig. 7 is a cross-sectional view showing still another example of the method of forming a functional porous body on a substrate of the present invention. Fig. 8 is a view showing a part of the steps of producing a functional porous body using the gel-containing pulverized liquid of the present invention and another example of the apparatus used therein. Fig. 9 is a view schematically showing a part of the steps of producing a functional porous body using the gel-containing pulverized liquid of the present invention and another example of the apparatus used therein.

no

Claims (9)

A method for producing a gel-containing pulverized liquid, comprising the steps of: a gel manufacturing step for producing a gel, a solvent replacement step of replacing a solvent in the gel with another solvent, and the gel a gel grinding step of pulverizing in the other solvent; the manufacturing method is performed by dividing the pulverizing step into a plurality of pulverizing steps; and after the solvent replacing step and before the start of the first pulverizing step, a concentration adjusting step is further included to perform the above-mentioned The concentration of the liquid of the gel is adjusted; and the concentration adjustment of the gel-containing liquid is not performed immediately after the start of the initial pulverization stage. The manufacturing method of claim 1, wherein the plurality of pulverizing stages include a first pulverizing stage and a second pulverizing stage for pulverizing the gel, and the first pulverizing stage is pulverizing the gel to a volume average particle diameter of 0.5. In the stage of the particles of ~100 μm, the second pulverization stage is a stage in which the particles are further pulverized into particles having a volume average particle diameter of 10 to 1000 nm after the first pulverization step. The method of claim 2, wherein after the first pulverization stage, the shear viscosity of the liquid containing the particles is 50 mPa ∙ s or more, and the volume average particle diameter of the particles is 0.5 to 50 μm. The production method according to any one of claims 1 to 3, wherein in the concentration adjustment step, the gel concentration of the gel-containing liquid is adjusted to 1 to 5% by weight. The production method according to any one of claims 1 to 4, wherein in the gel pulverizing step, the weight of the gel-containing liquid is from the beginning of the initial pulverization phase until the end of the final pulverization phase. The % concentration change is within ±3%. The manufacturing method according to any one of claims 1 to 5, further comprising a gel form controlling step of controlling the shape and size of the gel before the solvent replacement step. The method according to claim 6, wherein in the gel form control step, the gel is controlled into a three-dimensional object having a short diameter of 0.5 cm or more and a long diameter of 30 cm or less. The manufacturing method according to claim 6, wherein in the gel form control step, the gel is controlled into a rectangular parallelepiped having a short side of 0.5 cm or more and a long side of 30 cm or less. The manufacturing method according to any one of claims 1 to 8, wherein after the end of the initial pulverization phase and before the end of the final pulverization phase, the gel concentration of the gel-containing liquid is measured, and only the gel concentration is The aforementioned liquid in a predetermined number of ranges is supplied to the subsequent pulverization stage