TW201628998A - Void structured film bonded through catalytic action and method for manufacturing same - Google Patents

Abstract

The purpose of the present invention is to provide, for example, a void structured film in which a porous structure with a high porosity is formed while preventing cracking and which has a high strength. The void structured film according to the present invention is characterized in that one or more kinds of structural units for forming a microvoid structure are chemically bonded together through a catalytic action. The void structured film according to the present invention has an excoriation resistance of 60-100% when measured by using, for example, BEMCOT (registered trademark) and the number of times of folding endurance in an MIT test of 100 or greater. The void structured film can be manufactured by forming a precursor of a porous silicone body with the use of, for example, a sol containing ground pieces of a gel-type silicon compound, and then chemically bonding the ground pieces contained in the precursor of the porous silicone body. It is preferred that the ground pieces are chemically bonded together through, for example, chemical cross-linking.

Description

Void structure film combined by catalytic action and manufacturing method thereof Field of invention

The present invention relates to a void structure film bonded by a catalytic action and a method of producing the same.

Background of the invention

As for the porous structure, various examples of various materials and methods can be used, and they are applied to a wide range of products, such as optical members such as a low refractive index layer, a heat insulating material, a sound absorbing material, and a substrate for regenerative medical treatment. In the porous structure, there is a definition in a dispersed state in which a closed-cell structure and an open-cell structure are present, and the hermetic foamed structure is a single void (empty The pores are formed by dispersion, and the open foam structure is formed by the formation of the above-mentioned airtight foam structure. In addition, there are also definitions of void size or various porous structures.

The method for producing such a porous structure is as follows: by substituting a solvent contained in the wet gel with a gas under supercritical conditions, the skeleton structure of the wet gel is directly frozen and not shrinked. A method of drying a gel (for example, refer to Patent Document 1). The dried gel body can be classified into a dry gel which slowly evaporates and removes the gel solvent under normal pressure, and an "air-like gel" which is a low bulk density and a high porosity, that is, an aerogel.

In general, when producing a porous structure of an aerogel, the problem is how to prevent cracking of the gel when the gel is dried. The above-mentioned cracking occurs when the tensile stress caused by the capillary force of the surface tension of the solution remaining in the pores of the gel in the drying is larger than the gel strength. Under the supercritical condition, although the crack-free porous structure can be obtained by the disappearance of the surface tension, it is possible to cause cracking during the high-temperature sintering treatment as a process of removing the large pores. In order to suppress the occurrence of cracks during such high-temperature treatment, in some cases, a solvent having a boiling point higher than that of water and having a small surface tension or a fine particle of cerium oxide is used (Non-Patent Document 1).

On the other hand, when a structure having a high void ratio is formed, the skeleton density of the structure is lowered, so that the strength is remarkably lowered. As the strength is lowered, there is a problem in use such as low scratch resistance. In this regard, for example, a method of firing a polysiloxane porous body to increase the strength when the constituent material constituting the void structure is a polysiloxane porous material has been disclosed (see, for example, Patent Documents 2 to 5). However, in order to carry out high-temperature treatment at 200 ° C or higher for a long period of time in the firing treatment, batch processing is a prerequisite, and continuous production cannot be performed industrially. Further, when the calcination treatment is carried out, the crystal stable phase of the cerium oxide gel is transferred from the low-temperature phase phase to the high-temperature phase, and when the sintering is completed and the cooling is performed, there is a problem that cracks occur due to a large volume change. The same phenomenon is not limited to the cerium oxide gel, and can be confirmed by various constituent materials forming the void structure.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2005-154195

Patent Document 2: Japanese Patent Laid-Open No. 2006-297329

Patent Document 3: Japanese Patent Laid-Open No. 2006-221144

Patent Document 4: Japanese Patent Laid-Open No. 2006-011175

Patent Document 5: Japanese Patent Laid-Open Publication No. 2008-040171

Non-patent literature

Non-Patent Document 1: T. Adachi, J. Mater. Sci., 22.4407-4410 (1987)

Summary of invention

Accordingly, an object of the present invention is to provide a void structure film which can suppress the generation of cracks and which can form a porous structure having a high void ratio and which also has strength, and a method for producing the same.

In order to achieve the above object, the void structure film of the present invention is characterized in that one or more constituent units capable of forming a fine void structure are chemically bonded to each other via a catalytic action. Hereinafter, a void layer (void structure film) of a porous body in which the microporous particles of polyoxymethylene are directly or indirectly chemically bonded to each other will be mainly described. In addition, the void structure film of the present invention of the porous polysiloxane body may be referred to as "the porous polysiloxane body of the present invention" hereinafter.

The method for producing a polysiloxane porous body of the present invention is characterized by comprising the steps of: preparing a liquid containing fine pore particles of a ruthenium compound; The catalyst is added to the liquid, and the catalyst is used for chemically bonding the fine pore particles of the ruthenium compound to each other; and a bonding step of chemically bonding the microporous particles to each other via a catalyst.

However, the void structure film of the present invention and the polysiloxane porous body of the present invention are not limited by this production method, and can be produced by any production method.

The void structure film of the present invention is as described above, and one or more constituent units capable of forming a fine void structure are chemically bonded to each other via a catalytic action. For example, in the porous polysiloxane system of the present invention, the fine pore particles of the ruthenium compound are used, and the microporous particles of the ruthenium compound are chemically bonded to each other via a catalyst to immobilize the porous structure. Thereby, it is possible to provide a void structure film which can suppress the generation of cracks (cracks) while forming a porous structure having a high void ratio and also having strength.

10‧‧‧Substrate

20‧‧‧Porous structure

20'‧‧‧ coated film (precursor layer)

20”‧‧‧Sol particle liquid

21‧‧‧Strengthened porous structure (porous body)

101, 201‧‧‧Send rolls

102‧‧‧Application roller

105, 251‧‧ ‧ take-up rolls

106‧‧‧Roll parts

110, 210‧‧‧ oven area

111, 131, 231‧‧‧Hot air heaters (heating mechanism)

120, 220‧‧ ‧ chemical treatment area

121, 221‧‧‧ lamps (light irradiation mechanism) or air heater (heating mechanism)

130a, 230a‧‧‧ adhesive layer coating area

130, 230‧‧‧ intermediate formation area

131a, 231a‧‧‧ adhesive layer coating mechanism

202‧‧‧Liquid storage area

203‧‧‧Doctor knife

204‧‧‧ microgravure

211‧‧‧ heating mechanism

Fig. 1 is a cross-sectional view showing an example of a method of forming a porous polysiloxane porous body 20 on a substrate 10 in the present invention.

Fig. 2 is a view schematically showing a part of the steps in the method for producing the void structure film of the present invention and an example of the apparatus used therefor.

Fig. 3 is a view schematically showing a part of the steps in the method for producing the void structure film of the present invention and another example of the apparatus used therefor.

Fig. 4 is a cross-sectional SEM image of the porous polysiloxane body of the example.

Fig. 5 is a TEM image of a fine pore particle of the porous polysiloxane porous body of the example.

Figure 6 is a cross-sectional view showing the present invention on a substrate Another example of a method of forming a polysiloxane porous body.

Fig. 7 is a view schematically showing a part of the steps in the method for producing the void structure film of the present invention and another example of the apparatus used therefor.

Fig. 8 is a view schematically showing a part of the steps in the method for producing the void structure film of the present invention and another example of the apparatus used therefor.

Figure 9 is a cross-sectional view showing still another example of the method of forming a porous polysiloxane body on a substrate in the present invention.

Fig. 10 is a view schematically showing a part of the steps in the method for producing the void structure film of the present invention and another example of the apparatus used therefor.

Figure 11 is a view schematically showing a part of the steps in the method for producing the void structure film of the present invention and another example of the apparatus used therefor.

Form for implementing the invention

The polyfluorene-containing porous system of the present invention has, for example, an open structure in which the porous structure is a continuous foamed structure in which a pore structure is continuously formed.

In the production method of the present invention, for example, the catalyst is a catalyst that promotes crosslinking and bonding of the cerium compound sols to each other.

Hereinafter, the present invention will be further specifically described by way of examples. However, the invention is not limited or limited by the following description.

In the void structure film of the present invention, for example, the bond of the above constituent units may contain a hydrogen bond or a covalent bond. The constituent unit forming the void structure film of the present invention may be configured, for example, by 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. In addition, the aforementioned particulate constituent unit The constituent element 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, polyfluorene oxide particles or polycrystalline oxygen particles having fine pores, hollow cerium oxide nanoparticles or hollow cerium oxide may be mentioned. Nanoballoon and so on. The fibrous constituent unit is, for example, a nanofiber having a diameter of a nanometer, and specific examples thereof include cellulose nanofibers and alumina nanofibers. The structural unit of the flat plate may, for example, be a nano-clay, and specifically, a bentonite of a nanometer size (for example, Kunipia F [trade name]) may be mentioned. The fibrous constituent unit is not particularly limited, and may be, for example, selected from the group consisting of carbon nanofibers, cellulose nanofibers, alumina nanofibers, chitin nanofibers, chitin nanofibers, and polymer nanometers. At least one fibrous substance in the group consisting of fibers, glass nanofibers, and cerium oxide nanofibers. Further, the void structure film of the present invention contains a portion in which one or more constituent units capable of forming the aforementioned fine void structure are chemically bonded to each other via a catalytic action, for example, directly or indirectly. Further, in the above-described void structure film of the present invention, at least a part of the one or more constituent units may be chemically bonded via a catalytic action. Specifically, it is as if there is a portion where the constituent units are not chemically bonded even if they are in contact with each other. Further, in the present invention, the "indirect bonding" of the constituent units means that the constituent units are bonded to each other through a small amount of the binder component of the constituent unit or less. The "direct bonding" of the constituent units means that the constituent units are directly bonded to each other without being passed through the binder component or the like.

[1. Void structure film]

Hereinafter, the void structure film of the present invention is mainly composed of the present invention. The porous oxygen-containing body is described as a center. However, as described above, the void structure film of the present invention is not limited to only the polysiloxane porous body. Further, as described above, the void structure film of the present invention has a porous structure having a high void ratio and suppressing the occurrence of cracks (cracks) as well as the above, and has an effect of strength.

As described above, the porous polysiloxane body of the present invention is characterized by containing fine pore particles of a ruthenium compound and the fine pore particles of the ruthenium compound are chemically bonded to each other via a catalyst. In the present invention, the shape of the "particles" (for example, the fine pore particles of the ruthenium compound) is not particularly limited, and may be, for example, a spherical shape or an aspherical system.

The polyasperylene porous body of the present invention has a three-dimensional structure because the fine pore particles of the above ruthenium compound are chemically bonded (for example, crosslinked) via a catalyst. With such a configuration, the porous polysiloxane porous body of the present invention has a structure having a void, but can maintain a sufficient total strength and sufficient flexibility to suppress cracking. Therefore, the polysiloxane porous body of the present invention can be used for various members as a film body of a porous structure, for example. Specifically, the porous polysiloxane body of the present invention can be used, for example, as an optical member such as a low refractive index layer, a heat insulating material, a sound absorbing material, a substrate for regenerative medical treatment, a dew condensation preventing material, an ink image receiving material, or the like. The polysiloxane porous body of the present invention is particularly preferably a dry gel, but may differ depending on, for example, the use or purpose. Conventionally, although a dry gel has excellent strength but a low void ratio, on the other hand, an aerogel has a high void ratio but a low strength. In contrast, the porous polysiloxane body of the present invention has both high void ratio and strength. That is, the porous polysiloxane porous body of the present invention can achieve a high void ratio similarly to an aerogel even if it is a dry gel. In addition, in this issue In the polysiloxane porous body, the fine pore particles of the ruthenium compound are preferably a pulverized product of a gelatinous ruthenium compound. By the pulverized material of the gelatinous cerium compound, a completely new three-dimensional structure which is distinct from the unpulverized gelatinous quinone compound can be formed, and the pulverized materials can be chemically bonded to each other (for example, crosslinked). Thereby, the porous polysiloxane porous body of the present invention can exhibit physical properties different from those of the unpulverized gelatinous quinone compound (for example, the above-described sufficient strength, sufficient flexibility, and the like). Further, in the present invention, the fine pore particles of the ruthenium compound may be, for example, sol-gel beaded particles, nano particles (hollow nano cerium oxide/nanosphere particles), or nanofibers.

As described above, the porous polysiloxane body of the present invention contains fine pore particles (preferably a pulverized product of a gelatinous ruthenium compound) of the ruthenium compound, and the fine pore particles of the ruthenium compound are chemically bonded to each other via a catalyst. In the porous polysiloxane body of the present invention, the chemical bonding (chemical bond) form of the fine pore particles of the ruthenium compound is not particularly limited, and specific examples of the chemical bond include a crosslinking bond. Further, a method of chemically bonding the fine pore particles of the above ruthenium compound to each other will be described in detail in the production method of the present invention.

The aforementioned crosslinking bond is, for example, a decane bond. However, the chemical bond of the present invention is not limited to the decane structure. 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 the aforementioned decane bond, for example, it may have any one of the bonds, may have any two of them, or may have all three of the 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, the aforementioned ratio of T4 in the alkane bond is more than The intensity is revealed, but the gap size becomes small and the flexibility becomes weak. Therefore, the T2, T3, and T4 ratios should be changed depending on, for example, the use.

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

Further, the porous polysiloxane porous body of the present invention is preferably bonded to a helium atom, for example, by a helium atom. In a specific example, the ratio of the undoped ruthenium atoms (that is, the residual stanol) in the total ruthenium atoms contained in the porous polysiloxane porous body is, for example, less than 50%, 30% or less, and 15% or less.

The fine pore particles of the ruthenium compound are not particularly limited, and the pulverized product of the gelatinous ruthenium compound is preferably used as described above. The gel form of the gelled quinone compound 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 former As the gelatinous quinone compound, for example, a wet gel is preferably used.

The void structure film of the present invention (representing the polyoxynitride porous body of the present invention, hereinafter the same) has, for example, a pore structure, and the pore size of the pores means the length of the major axis diameter and the minor axis diameter of the void (hole). Shaft diameter. The ideal pore size is, for example, 5 nm to 10 cm. The lower limit of the gap 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, 10 cm or less, 1 mm or less, or 1 μm or less, and the range thereof is, for example, 5 nm to 10 cm, 10 nm to 1 mm, and 20 nm to 1 μm. The size of the voids is determined by the use of the void structure to determine the appropriate void size, for example, the desired void size must be adjusted for the purpose. Further, a preferred embodiment of the pore structure of the void structure film of the present invention is shown in Fig. 4 (cross-sectional SEM image) of the later-described embodiment. However, FIG. 4 is an example and does not limit the present invention in any way. Further, the void size can be evaluated, for example, by the following method.

(SEM observation of cross section of void structure film)

In the present invention, the morphology of the void structure film can be observed and analyzed by SEM (Scanning Electron Microscope). Specifically, for example, a porous stanol sample formed on a resin film can be processed by cooling down FIB (acceleration voltage: 30 kV), and the obtained cross-section sample is obtained by FIB-SEM (trade name: Helios, manufactured by FEI). NanoLab 600, acceleration voltage: 1 kV) Obtained cross-sectional electron image at an observation magnification of 100,000 times.

(evaluation of void size)

In the present invention, the aforementioned void size can be quantified by the BET test method. Specifically, it is a capillary input sample (a void junction of the present invention) of a specific surface area measuring device (manufactured by Micromeritics Co.: trade name: ASAP2020). After 0.1 g of the film structure, the film was dried under reduced pressure at room temperature for 24 hours to degas the gas in the void structure. Nitrogen gas was then adsorbed onto the aforementioned sample, and an adsorption isotherm was drawn to calculate the pore distribution. This allows the gap size to be evaluated.

The void structure film of the present invention has a scratch resistance of, for example, 60 to 100% by using Bemcot (registered trademark). The aforementioned scratch resistance means the strength of, for example, film strength. The present invention has excellent scratch resistance in various processes, for example, because of such strength. The present invention has scratch resistance in a production process for winding and handling a film of a product after the formation of the above-mentioned void structure film, for example. Further, the void structure film of the present invention can increase the film strength by, for example, adjusting the film density. Specifically, the microporous particles of the cerium compound (preferably cerium oxide sol fine particles, preferably cerium oxide sol fine particles obtained by pulverizing the gelled cerium oxide compound) can be used by the catalyst reaction in the heating step described later. The stanol group undergoes a crosslinking reaction to increase the binding force of the fine pore particles of the ruthenium compound. By adjusting the amount of residual stanol groups and the balance of the crosslinking reaction, the porosity can be controlled while imparting strength to the film. Thereby, the porous polysiloxane body of the present invention can impart a certain degree of strength to, for example, an originally weak void structure.

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% or 80%. 99%, 90~98%.

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

(evaluation of scratch resistance)

(1) A void layer (the void structure film of the present invention) which is coated and formed on an acrylic film is sampled into a round shape having a diameter of about 15 mm.

(2) Next, 矽 was identified by fluorescent X-ray (ZSX Primus II, manufactured by Shimadzu Corporation) to measure the Si coating amount (Si ₀ ). Then, the void layer on the acrylic film was cut into 50 mm × 100 mm from the circumference of the sample and fixed to a glass plate (thickness: 3 mm), and then subjected to a sliding test by Bemcot (registered trademark). The sliding condition is set to a weight of 100 g and 10 reciprocating.

(3) Sampling and fluorescence X measurement were performed in the same manner as in the above (1) from the gap layer which was finished sliding, and the Si residual amount (Si ₁ ) after the scratch test was measured. The scratch resistance is defined by the Si residual ratio (%) before and after the sliding test by Bemcot (registered trademark), and can be expressed by the following formula.

Scratch resistance (%) = [remaining Si amount (Si ₁ ) / Si coating amount (Si ₀ )] × 100 (%)

The void structure film of the present invention has a folding endurance of, for example, 100 times or more by the MIT test. The aforementioned number of folding resistances means flexibility, and flexibility means, for example, the deformability of the substance. Since the present invention has such flexibility, it is possible to suppress the occurrence of cracks as described above, and is excellent in handleability such as winding at the time of production or use.

The lower limit of the number of times of folding is, for example, 100 or more, 500 or more, or 1,000 or more, and the upper limit is not particularly limited, and is, for example, 10,000 or less, and the range is, for example, 100 to 10,000 times and 500 to 10,000 times. 1000~10000 times.

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)

Cutting the aforementioned void layer (the void structure film of the present invention) into After a short strip of 20 mm × 80 mm, it was mounted on an MIT folding tester (BE-202, manufactured by TESTER SANGYO CO., LTD.), and a load of 1.0 N was applied. The chuck portion in which the gap layer is sandwiched is R2.0 mm, and the folding endurance is performed at most 10,000 times, and the number of times when the gap layer is broken is used as the folding end number.

In the void structure film of the present invention, the film density is not particularly limited, and the lower limit thereof is, for example, 1 g/cm ³ or more, 10 g/cm ³ or more, 15 g/cm ³ or more, and the upper limit thereof is, for example, 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 , 15 to 30 g/cm ³ , and 1 to 2.1 g/cm ³ . Further, in the void structure film of the present invention, the porosity obtained by the film density is not particularly limited, and the lower limit thereof is, for example, 40% or more, 50% or more, 70% or more, 85% or more, and the upper limit thereof is, for example, 98%. Hereinafter, the range is 95% or less, and the range is, for example, 40 to 98%, 50 to 95%, 70 to 95%, and 85 to 95%.

The film density can be measured, for example, by the following method, and the porosity can be calculated, for example, in the following manner according to the film density.

(Evaluation of membrane density and porosity)

After forming a void layer (the void structure film of the present invention) on the substrate (acrylic film), the X-ray diffraction apparatus (RINT-2000, manufactured by RIGAKU Co., Ltd.) was used to measure the X of the total reflection region with respect to the void layer of the laminate. Radiation reflectance. Then, after the Intensity and 2θ were prepared, the film density (g/cm ³ ) was calculated from the total reflection critical angle of the laminate (void layer ‧ substrate), and the porosity (P%) was calculated by the following formula.

Porosity (P%) = 45.48 × film density (g / cm ³ ) + 100 (%)

The void structure film of the present invention may have a pore structure (porous structure) as described above, and may be, for example, an open foam structure in which the pore structure is continuously formed. The open foam structure is, for example, a state in which the pore structure is connected in a three-dimensional state in the void structure film, and it can be said that the internal pores of the pore structure are connected together. When the porous body has an open foam structure, the porosity of the void structure film can be increased, and when the airtight pores such as hollow cerium oxide are used, an open foam structure cannot be formed. On the other hand, in the porous polysiloxane body of the present invention, the fine pore particles of the cerium compound (ideally, the cerium oxide sol fine particles are preferably cerium oxide sol fine particles of the pulverized cerium compound forming a sol). Since the three-dimensional tree structure is provided, for example, in the coating process, the coating film (the coating film containing the sol of the cerium oxide sol fine particles) can be easily formed into an open hair by the deposition of the aforementioned dendritic particles. Bubble structure. Further, the void structure film of the present invention desirably forms a monolith structure in which an open foam structure has a plurality of pore distributions. The above monolithic structure refers to, for example, a structure having fine voids of a nanometer size and a hierarchical structure in which an open foamed structure formed by the same nanovoids exists. When the monolithic structure is formed, for example, the strength can be imparted by the fine voids, and the high porosity can be imparted by the coarse open foaming voids, and the strength and the high porosity can be simultaneously established. In order to form a monolithic structure such as, for example, it is preferable to first control the pore distribution of the void structure to be formed in the gel (gel-like cerium compound) in the stage before the pulverization into the cerium oxide sol fine particles. Further, when the gel-like cerium compound is pulverized, for example, the particle size distribution of the pulverized cerium oxide sol fine particles can be controlled to a desired size to form The aforementioned monolithic structure.

In the void structure film of the present invention, the haze exhibiting 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, 30% or less, 10% or less, or 3% or less. The range is, for example, 0.1 to 30%, 0.2 to 10%, and 0.3 to 3%.

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

(evaluation of haze)

The void layer (the void structure film of the present invention) was cut into a size of 50 mm × 50 mm and attached to a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.: HM-150), and the haze was measured. The haze value can be calculated by the following formula.

Haze (%) = [Diffuse Transmittance (%) / 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 void structure film of the present invention is not particularly limited, and the upper limit thereof is, for example, 1.25 or less, 1.20 or less, or 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, and the range is, for example, 1.05 or more and 1.25 or less. 1.06 or more ~ 1.20 or less, 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 can be measured, for example, by the following method.

(evaluation of refractive index)

After forming a void layer (the void structure film of the present invention) on the acrylic film, it was cut into a size of 50 mm × 50 mm and adhered to the surface of the glass plate (thickness: 3 mm) with an adhesive layer. The center of the back surface of the aforementioned glass plate (diameter A sample of about 20 mm was blackened with a black microphone pen to prepare a sample that would not be 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 value thereof was used as the refractive index.

The thickness of the void structure film of the present invention is not particularly limited, and the lower limit thereof is, for example, 1 nm or more, 10 nm or more, 50 nm or more, or 100 nm or more, and the upper limit thereof is, for example, 1000 μm or less, 500 μm or less, 100 μm or less, or 80 μm or less, and the range is, for example, 1 nm to 1000 μm, 10 nm to 500 μm, 50 nm to 100 μm, and 100 nm to 80 μm. In the case of a film body, it can be adjusted according to the use or required characteristics. For example, when the transmittance is important, it is preferably 0.01 μm or more and 10 μm or less. For example, when the heat insulating property is important, it is 100 μm or more and 1 m or less. good.

The gelled ruthenium compound may be a gelled product obtained by gelling a monomer ruthenium compound. Specifically, the gel-like ruthenium compound may, for example, be a gelled product in which the above-mentioned monomer ruthenium compounds are bonded to each other, and specific examples thereof may be such that the above-mentioned monomer ruthenium compounds form a hydrogen bond or an intermolecular force. Gelled. The foregoing combination may be exemplified by a combination of dehydration condensation. The method of gelling described above will be described later in the production method of the present invention.

In the present invention, the above monomer ruthenium compound is not particularly limited. The monomer oxime compound may be a compound represented by the following formula (1). When the gelled quinone compound is a gelled product in which the above-mentioned monomer quinone compound is hydrogen-bonded or intermolecularly bonded to each other, the monomer of the formula (1) can be hydrogen-bonded, for example, through each of the hydroxyl groups.

In the above formula (1), for example, X is 2, 3 or 4, and R ¹ is a linear alkyl group or a branched alkyl group. The carbon number of R ^{1 is} , for example, 1 to 6, 1 to 4, or 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 hydrazine (hydroxy)methyl decane. When X is 3, the above hydrazine compound is, for example, a trifunctional decane having three functional groups.

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 monomer oxime compound may be, for example, a hydrolyzate of a ruthenium compound precursor. As the precursor of the ruthenium compound, for example, the ruthenium compound can be produced by hydrolysis, and specific examples thereof include the following formula. (2) The compound shown.

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

X and R, for example, the same as in the above formula (1) of X ¹ and R ^1. Further, the aforementioned R ² may be exemplified by, for example, R ¹ of the formula (1).

Specific examples of the ruthenium compound precursor 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 ruthenium compound precursor is trimethoxy(methyl)decane (hereinafter also referred to as "MTMS").

The monomer oxime compound is not particularly limited, and can be suitably selected, for example, according to the use of the polysiloxane porous body of the present invention. In the polyaluminum oxide porous body of the present invention, for example, in the case where the low refractive index property is emphasized, the monomeric ruthenium compound is preferably the above-mentioned trifunctional decane based on the viewpoint of good low refractive index; Moreover, when importance is attached to strength (for example, scratch resistance), it is preferable that the monomer bismuth compound is preferably the above-mentioned tetrafunctional decane based on the scratch resistance. On the other hand, when flexibility is desired, it is preferable to use the above-mentioned bifunctional decane based on flexibility. In addition, the monomer oxime compound which is a raw material of the above-mentioned gelatinous ruthenium compound 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 as the monomer quinone compound, the ratio thereof is not particularly limited, and can be appropriately set.

In the porous polysiloxane body of the present invention, the volume average particle diameter indicating the particle size deviation of the fine pore particles (preferably the pulverized product of the gelled cerium oxide compound) of the cerium compound is not particularly limited, and the lower limit thereof is, for example, 0.05. The upper limit is, for example, 0.050 μm or less, 1.50 μm or less, or 1.00 μm or less, and the range is, for example, 0.05 μm to 2.00 μm, 0.10 μm to 1.50 μm, and 0.20 μm to 1.00 μm. The particle size distribution can be carried out, for example, by a particle size distribution evaluation device such as a light centrifugal sedimentation method, 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). Determination, but not limited by these methods. Further, in the present invention, the fine pore particles of the ruthenium compound may be shaped or amorphous. Further, each of the fine pore particles of the above ruthenium compound preferably has a single or a plurality of fine pores. In the present invention, a suitable form of the fine pore particles of the ruthenium compound is as shown in Fig. 5 (TEM image) of the later-described embodiment. However, Figure 5 is an example. The invention is defined. Further, in the present invention, the TEM image of the fine pore particles of the ruthenium compound can be observed, for example, by the following method.

(TEM observation of microporous particles)

In the present invention, the form of the fine pore particles of the ruthenium compound can be observed and analyzed by TEM (transmission electron microscope). Specifically, the dispersion of the fine pore particles of the ruthenium compound is diluted to an appropriate concentration, and then dispersed on a carbon support and dried to obtain a sample of fine pore particles. Then, the sample was obtained by TEM (manufactured by Hitachi, Ltd., trade name H-7650, acceleration voltage: 100 kV) at an observation magnification of 100,000 times.

Further, the particle size distribution indicating the particle size variation of the fine pore particles of the ruthenium compound is not particularly limited, and for example, particles having a particle diameter of 0.4 μm to 1 μm are 50 to 99.9% by weight, 80 to 99.8% by weight, and 90 to 99.7% by weight, or The particles having a particle diameter of 1 μm to 2 μm are 0.1 to 50% by weight, 0.2 to 20% by weight, and 0.3 to 10% by weight. The aforementioned particle size distribution can be determined, for example, by a particle size distribution evaluation device or an electron microscope.

The void structure film of the present invention may, for example, contain a catalyst for chemically bonding one or more constituent units forming the aforementioned fine void structure to each other. The content of the 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 constituent unit.

Further, the void structure film of the present invention may further contain, for example, a crosslinking auxiliary agent for indirectly bonding one or more constituent units forming the aforementioned fine void structure to each other. The aforementioned crosslinking auxiliary agent The rate 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 constituent unit.

The form of the void structure film of the present invention is not particularly limited, and may be, for example, a film shape.

The method for producing the void structure film of the present invention is not particularly limited, and can be produced, for example, by the production method of the present invention shown below.

[2. Method for producing void structure film]

Hereinafter, the method for producing the void structure film of the present invention will be mainly described focusing on the method for producing a porous porous oxygen body of the present invention. As described above, the method for producing a polysiloxane porous body according to the present invention includes the steps of: preparing a liquid containing fine pore particles of a ruthenium compound; and adding a catalyst for chemically bonding the fine pore particles to each other in the liquid; And a bonding step of chemically bonding the aforementioned fine pore particles to each other by a catalyst. The liquid containing the fine pore particles of the ruthenium compound is not particularly limited, and may be, for example, a suspension containing fine pore particles of the ruthenium compound. Further, as described above, the fine pore particles of the cerium compound are preferably a pulverized product of a gelled cerium oxide compound. In the following, the case where the fine pore particles of the cerium compound are a pulverized product of a gelled cerium oxide compound (hereinafter sometimes referred to simply as "pulverized material") will be described. In the method for producing a porous polysiloxane body of the present invention, fine particles other than the pulverized product of the gel-like cerium oxide compound can be used as the fine pore particles of the cerium compound. Further, a method of producing a porous polysiloxane material from a substance other than a solution containing fine pore particles may be employed. For example, a dry film formation method such as aerosol deposition (AD method) may be used to laminate a pulverized material on a substrate. Polyoxyl Porous body.

According to the production method of the present invention, a porous porous structure having a porous structure capable of suppressing generation of cracks while forming a high void ratio and having sufficient strength can be formed. The reason for this is presumed as follows, but the present invention is not limited by this speculation.

In the pulverized product used in the production method of the present invention, the gel-like ruthenium compound is pulverized, and the three-dimensional structure of the gel-like ruthenium compound before the pulverization is dispersed into a three-dimensional basic structure. Further, in the production method of the present invention, the three-dimensional basic structure is deposited by using a sol containing the pulverized material of the gelatinous ruthenium compound, and a porous structure mainly composed of the three-dimensional basic structure is formed. That is, by the production method of the present invention, a novel porous structure which is distinct from the three-dimensional structure of the aforementioned gel-like cerium compound and which is formed of the aforementioned pulverized material of the above-described three-dimensional basic structure can be formed. Further, in the production method of the present invention, in order to further chemically bond the pulverized materials to each other, the novel three-dimensional structure is fixed. Therefore, the porous polysiloxane porous body obtained by the production method of the present invention has a structure having a void, and can still maintain the effect of suppressing the occurrence of cracks while achieving sufficient strength. According to the production method of the present invention, for example, the porous polysiloxane porous body can be formed as an additional member corresponding to various objects. The polysiloxane porous body obtained by the present invention can be applied, for example, as a member using voids in a wide range of articles, such as an optical member such as a low refractive index layer, a heat insulating material, a sound absorbing material, a regenerative medical substrate, and condensation. Preventing materials, ink image receiving materials, etc., can also be used to produce laminated films that impart various functions.

The production method of the present invention can be followed by the description of the porous polysiloxane body of the present invention, unless otherwise specified. The present invention can be utilized in the manufacture of any gel, for example, depending on the purpose and purpose, and is particularly advantageous for the manufacture of xerogels. Further, as described above, with the porous polysiloxane porous body of the present invention, even if it is a dry gel, a high void ratio can be achieved similarly as an aerogel.

In the production method of the present invention, the gel-like ruthenium compound and the pulverized product thereof, the monomer ruthenium compound and the ruthenium compound precursor may all be described in the above-described polyfluorinated porous body of the present invention.

The production method of the present invention has a step of preparing a liquid (preferably a sol containing the pulverized product of the gelatinous ruthenium compound) containing the fine pore particles of the ruthenium compound. The pulverized material can be obtained, for example, by pulverizing the gelatinous quinone compound. As described above, by pulverizing the gelatinous quinone compound, the three-dimensional structure of the gelatinous quinone compound is destroyed and dispersed into a three-dimensional basic structure.

In the following, the gelatinized compound is produced by gelation of the above-mentioned hydrazine compound, and the gelled quinone compound is pulverized to prepare a pulverized product, but the present invention is not limited by the following examples.

The gelation of the aforementioned hydrazine compound can be achieved, for example, by hydrogen-bonding or inter-molecular force bonding of the above-mentioned monomer quinone compounds.

The above-mentioned monomer oxime compound may be an oxime compound represented by the above formula (1) which has been mentioned in the above-mentioned polyfluorene oxide porous body of the present invention.

Since the oxime compound of the above formula (1) has a hydroxyl group, the monomers of the above formula (1) can be hydrogen-bonded or intermolecularly bonded, for example, through the respective hydroxyl groups.

Further, the ruthenium compound may be a hydrolyzate of the ruthenium compound precursor as described above, and for example, the ruthenium compound precursor represented by the above formula (2) mentioned in the above-mentioned polyfluorene oxide porous body of the present invention may be hydrolyzed. generate.

The hydrolysis method of the ruthenium compound precursor is not particularly limited, and for example, it can be carried out 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 and mixing an aqueous oxalic acid solution into a mixed liquid (for example, a suspension) of the above-mentioned hydrazine compound and dimethyl hydrazine at room temperature, followed by stirring for about 30 minutes in this state. 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 the subsequent gelation, aging, and heating after the formation of the void structure.

The gelation of the above monomer ruthenium compound can be carried out, for example, by a dehydration condensation reaction between the aforementioned monomers. The dehydration condensation reaction is preferably carried out, for example, in the presence of a catalyst. The catalyst may, for example, be a dehydration condensation catalyst such as an acid catalyst or a basic catalyst, and the acid catalyst may be hydrochloric acid, oxalic acid, sulfuric acid or the like, and the base may be used. The catalysts include ammonia, potassium hydroxide, sodium hydroxide, ammonium hydroxide and the like. The aforementioned dehydration condensation catalyst is preferably a basic catalyst. In the dehydration condensation reaction, the amount of the catalyst added to the monomer ruthenium compound is not particularly limited, and the catalyst is, for example, 0.1 to 10 mol, 0.05 to 7 with respect to the monomer oxime compound 1 mol. Moer, 0.1~5 m.

The gelation of the aforementioned monomer ruthenium compound is preferably carried out, for example, in a solvent. The ratio of the aforementioned hydrazine compound of 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 with respect to the solvent containing the ruthenium compound 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, or 10 to 30 minutes. When the dehydration condensation reaction described above is carried out, the treatment conditions thereof are not particularly limited, and the examples can be used. By performing the gelation described above, for example, a ceria can be bonded to form a ceria primary particle, and by the progress of the reaction, the primary particles can be connected to each other to form a bead to form a three-dimensional gel.

The aforementioned gelatinous quinone compound obtained by the gelation described above is preferably subjected to a ripening treatment after the gelation reaction. By the aforementioned ripening treatment, for example, the gel primary particles having a three-dimensional structure obtained by gelation are further grown, the size of the particles themselves can be increased, and as a result, the particles can be brought into contact with each other. The contact state of the neck is expanded from point contact to face contact. The gel subjected to the above-mentioned ripening treatment, for example, increases the strength of the gel itself, and as a result, the strength of the three-dimensional basic structure after the pulverization can be enhanced. Thereby, for example, in the drying step after the application of the pulverized material, the pore size of the void structure in which the three-dimensional basic structure is deposited can be suppressed from shrinking as the solvent of the drying process volatilizes.

The aforementioned ripening treatment can be carried out, for example, by cultivating the gelatinous quinone compound at a predetermined temperature for a predetermined time. The predetermined temperature is not particularly limited, and the lower limit thereof 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 is, for example, 30 to 80° C., 35 . ~75 ° C, 40 ~ 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, or 30 hours or shorter, and the range is, for example, 5 to 50 hours, 10 ~40 hours, 15~30 hours. Further, the main purpose of the optimum conditions for the ripening is, for example, to obtain an increase in the primary particle size of the ceria and an increase in the neck contact area. Further, it is preferable to consider the boiling point of the solvent to be used. For example, when the aging temperature is too high, the solvent is excessively volatilized, and further, problems such as concentration of the coating liquid (gel liquid) may cause the pores of the three-dimensional void structure to be closed. On the other hand, for example, if the aging temperature is too low, not only the effect obtained by the above-mentioned aging may not be sufficiently obtained, but the temperature deviation of the mass production process may increase, and a product having poor quality may be produced.

For the aging treatment, for example, the same solvent as the gelation treatment described above can be used. Specifically, it is preferred to directly carry out the reaction after the gel treatment (that is, the solvent containing the gelatin enthalpy). Finished after gelation The molar number of the residual stanol group contained in the gel (the gel-like ruthenium compound) to be treated is such that the alkoxy number of the added raw material (for example, the aforementioned ruthenium compound precursor) is 100. The upper limit of the ratio of the residual stanol group is, for example, 50% or less, 40% or less, or 30% or less, and the lower limit thereof is, for example, 1% or more, 3% or more, or 5% or more, and the range is, for example, 1 to 50%. 3~40%, 5~30%. For the purpose of increasing the hardness of the gel, for example, the lower the molar number of the residual stanol group, the better. Once the molar number of the stanol group is too high, for example, the void structure may not be maintained until the precursor of the polysiloxane porous body is crosslinked. On the other hand, when the molar number of the stanol group is too low, for example, the precursor may not be crosslinked before the polysiloxane porous body is bonded in the bonding step, and thus sufficient strength cannot be imparted. Further, in the case where the above is a stanol group, for example, when the monomer ruthenium compound has been modified with various reactive functional groups, the same phenomenon can be applied to each functional group.

After the monomer ruthenium compound is gelated in the solvent for gelation, the obtained gel-like ruthenium compound is pulverized. For the pulverization, for example, the gelatinous ruthenium compound in the solvent for gelation may be directly subjected to pulverization treatment, or the solvent for gelation may be replaced with another solvent, and then the gelatinous ruthenium compound in the other solvent may be subjected to the pulverization treatment. Crushing treatment. In addition, the catalyst used in the gelation reaction and the solvent used may remain after the ripening step. Therefore, when it is desired to reduce the gelation time (applicability period) of the liquid and the drying efficiency in the drying step, it is preferable to replace it with Other solvents. The other solvent described above is also referred to as "solvent solvent" hereinafter.

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

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, DMSO and methanol, DMSO and butanol, and the like. In this way, by replacing the solvent for gelation with the solvent for pulverization, for example, a more uniform coating film can be formed in the formation of a coating film to be described later.

The pulverization method of the gelled ruthenium compound is not particularly limited, but a high-pressure medium-free pulverization apparatus is preferably used. For example, it can be carried out by the following devices: an ultrasonic homogenizer, a high-speed rotary homogenizer, a high-pressure extrusion pulverizing device, other wet-type medium-free pulverizing devices using cavitation, or a pulverizing device that obliquely impacts liquids with each other at high pressure. Wait. A device for pulverizing a medium such as a ball mill or the like physically ruptures the void structure of the gel during pulverization. In contrast, a cavitation pulverizing device preferred by the present invention, such as a homogenizer, is a high-pressure ‧ high-speed shear by means of a medium-free method The shear force peels off the joint of the weaker cerium oxide sol particles which has been contained in the three-dimensional structure of the gel, and does not accompany the physical destruction of the medium. Thereby, the obtained three-dimensional structure of the sol can maintain a void structure having a certain range of particle size distribution in the sub-fine particle region, and further form a void structure by coating and drying. 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 have a particle size deviation as described above (for example, a volume average particle size or a particle size fraction) The pulverized material of the cloth is pulverized. It is assumed that when the amount of work such as the pulverization time and the strength is insufficient, for example, not only the coarse particles but also the fine pores cannot be formed, and the appearance defects may be increased, and high quality may not 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 size of the voids which are deposited after the coating is dried may be fine, and the desired porosity may not be achieved.

A liquid (for example, a suspension) containing the above-mentioned fine pore particles (pulverized product of a gelatinous ruthenium compound) can be produced in the above manner. 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 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 fine pore particles (the pulverized product of the gelatinous cerium compound). By the catalyst, for example, the microporous particles can be chemically bonded to each other in a bonding step to be described later. 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 reaction of the hydroxyl groups of the stanol groups by the above-mentioned catalyst, 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. The aforementioned microporous particles can be chemically bonded to each other (for example, crosslinked bonding) by the aforementioned photoactive catalyst, for example, without heating. Thereby, for example, shrinkage due to heating is not easily caused, so that a high void ratio can be maintained. In addition, in addition to the aforementioned catalyst, a substance capable of generating a catalyst may be used (catalyst generation) Or) or replace it. For example, the catalyst may be a crosslinking reaction accelerator, and the catalyst generator may be a substance that generates the crosslinking reaction accelerator. 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 acid or the photocatalyst generating agent is not particularly limited, and examples thereof include a photobase generator (catalyst which generates an alkaline catalyst by light irradiation) and a photoacid generator (a substance which generates an acid catalyst by light irradiation). Etc., and photobase agents are 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.), 4- A compound of piperidine 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) or a triarylsulfonium salt (trade name). CPI101A: San-Apro Ltd.), an aromatic onium salt (trade name Irgacure 250: Ciba Japan K.K.), and the like. Further, the catalyst for chemically bonding the fine pore particles to each other is not limited to the photoactive catalyst, and may be, for example, a thermally active catalyst such as urea. 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 catalysts are preferred. The catalyst for chemically bonding the fine pore particles to each other, for example, may be added to a sol particle liquid (for example, a suspension) containing the pulverized material (microporous particles) before being coated, or may be used as The above mixture is mixed with a solvent and used 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 various organic solvents, water, and a buffer solution. Further, the liquid which can form the void structure other than the fine pore particles may contain a catalyst which can generate radicals by heating or light irradiation other than the above-mentioned acid or alkali, and can select the optimum unit in accordance with the constituent unit of the void structure film. catalyst.

Further, for example, when the fine pore particles of the ruthenium compound are a pulverized product of a gelatinous ruthenium compound and the gelatinous ruthenium compound is obtained from a ruthenium compound containing at least a trifunctional or less saturated bond functional group, it can be produced. Further, after the liquid containing the fine pore particles of the above ruthenium compound, or in the production step, a crosslinking auxiliary agent for indirectly bonding the fine pore particles of the ruthenium compound to each other is further added. The cross-linking auxiliary agent allows particles which are slightly separated in distance to be combined with each other by entering the particles with each other and utilizing the interaction or combination of the particles and the cross-linking auxiliary agent. It can increase the strength efficiently. 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 auxiliary agent may be exemplified by bis(trimethoxyindolyl)ethane, bis(triethoxyindenyl)ethane, bis(trimethoxyindenyl)methane, bis(triethoxyindenyl)methane, and a 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 Alkenyl-1,2-diamine, cis-(3-trimethoxydecylpropyl)trimeric isocyanate, cis-(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 fine pore particles of the cerium compound.

The porous polysiloxane porous body can be formed, for example, by forming a coating film using a liquid containing a fine pore particle of the above-described cerium compound (preferably a sol containing the pulverized product of the gelatinous cerium compound). The coating of the fine pore particles of the above-mentioned cerium compound can be carried out, for example, by various coating methods described later, but is not limited thereto. Further, the coating film can be formed by directly applying a solvent containing the pulverized material to the substrate. Further, the porous body precursor, that is, the coating film before the bonding step described later may be, for example, a precursor film (or a precursor layer) corresponding to the above-described polyfluorinated porous body of the present invention. By forming the aforementioned coating film, for example, the pulverized material which is damaging the three-dimensional structure can be deposited and deposited to form a new three-dimensional structure.

The solvent (hereinafter also referred to as "solvent for coating") 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 130 ° C or lower. Specific examples thereof include IPA, ethanol, methanol, butanol, and the like, and the same as the solvent for pulverization described above. In the step of forming the coating film, for example, the pulverization solvent containing the pulverized material of the gelatinous cerium compound can be used as it is, in the step of forming the coating film.

In the step of forming the coating film, for example, fine pore particles (hereinafter also referred to as "sol particle liquid") of the above-mentioned cerium compound dispersed in the solvent are preferably applied to the substrate. The sol particle liquid of the present invention can be continuously formed into a void layer having a strength of a certain degree or more, for example, after being applied onto a substrate and dried, and then chemically crosslinked by a bonding step. In addition, the "sol" of the present invention refers to a state in which the three-dimensional structure of the gel is pulverized, and the cerium oxide sol particles having a three-dimensional structure in which a part of the void structure is held are dispersed in a solvent to exhibit fluidity.

The concentration of the fine pore particles of the ruthenium compound in the solvent is not particularly limited, and is, for example, 0.3 to 80% (v/v), 0.5 to 40% (v/v), and 1.0 to 10% (v/v). When the concentration of the pulverized material is too high, for example, the fluidity of the sol particle liquid may be remarkably lowered to cause condensate/coating at the time of coating. On the other hand, when the concentration of the fine pore particles of the ruthenium compound is too low, it takes a considerable amount of time to dry the solvent of the sol particle liquid, and the residual solvent immediately after drying is also increased, so that the porosity may be lowered.

The physical properties of the sol particle liquid are not particularly limited. The aforementioned sol The shear viscosity of the particle liquid is, for example, at a shear rate of 1000 l/s, a viscosity of 100 cPa·s or less, a viscosity of 10 cPa·s or less, and a viscosity of 1 cPa·s or less. When the shear viscosity is too high, for example, a scratch may occur, and a problem that the transfer rate of the gravure coating is lowered may occur. Conversely, once the shear viscosity is too low, for example, the wet coating thickness at the time of coating may not be thickened and the desired thickness may not be obtained after drying.

The amount of the fine pore particles of the ruthenium compound to be coated with respect to the base material is not particularly limited, and can be appropriately set, for example, in accordance with the desired thickness of the porous porous siloxane material. In a specific example, when the polyaluminum oxide porous body having a thickness of 0.1 to 1000 μm is formed, the coating amount of the pulverized material with respect to the base material is, for example, 0.01 to 60000 g, 0.1 to 1 m ² per area of the substrate. 5000g, 1~50g. The desired coating amount of the sol particle liquid is related to, for example, the liquid concentration or the coating method, and thus it is difficult to make a single definition. When productivity is considered, it is preferable to apply a thin layer as much as possible. When the amount of coating is too large, for example, the possibility of drying in a drying oven before the solvent is volatilized increases. Thereby, the nanosized pulverized sol particles are precipitated in a solvent, and before the formation of the void structure, the formation of the void structure may be hindered by the 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 the unevenness of the base material, the deviation of the hydrophilicity and the like, and the like.

After the pulverized material is applied onto the aforementioned substrate, the coating film may be subjected to a drying treatment. The drying treatment temperature of the present invention is characterized in that it can be processed from a lower temperature and is suitable for continuous production in a short time. By the aforementioned drying treatment, not only the aforementioned solvent in the aforementioned coating film can be removed (the aforementioned The purpose of the solvent contained in the sol particle liquid is to cause the sol particles to settle and deposit in the drying process to form a void structure. The temperature of the drying treatment is, for example, 50 to 200 ° 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. With regard to the drying treatment temperature and time, for example, in the case of continuous productivity or the appearance of high porosity, it is preferred to use 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, when the glass transition temperature of the substrate is close to the substrate, the substrate may be stretched in a drying oven and may be formed into a void structure immediately after coating. There are disadvantages such as cracks. On the other hand, if the conditions are too loose, for example, since the residual solvent is contained at the time of leaving the drying furnace, an appearance defect such as a scratch may occur when rubbing against the roller member in the next step.

On the other hand, the drying treatment may be, for example, natural drying, and may be 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 phenomenon of the void layer (the porous polysiloxane porous body), 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 drying treatment temperature can be changed according to the thickness of the porous stanol porous body and the type of the solvent.

The foregoing substrate is not particularly limited, and the stanol can be used for the purpose. The structure of the pores is divided into a porous body which does not use a substrate or a porous body formed on a substrate. For example, a base material made of a thermoplastic resin, a base material made of glass, an inorganic substrate typified by ruthenium, a plastic such as a thermosetting resin, a semiconductor, or the like, and a carbon fiber material represented by a carbon nanotube are used. Etc., but not subject to such restrictions. The form of the substrate may be, for example, a film or a sheet. The thermoplastic resin may, for example, be polyethylene terephthalate (PET), acrylic acid, cellulose acetate propionate (CAP), cycloolefin polymer (COP), triacetate (TAC), polynaphthalene dicarboxylic acid. A highly transparent substrate such as ethylene glycol (PEN), polyethylene (PE), or polypropylene (PP).

In the production method of the present invention, the bonding step is a step of chemically bonding the fine pore particles of the cerium compound contained in the coating film to each other, and both the wet treatment and the dry treatment are suitably treated. By the above-described bonding step, for example, the three-dimensional structure of the fine pore particles of the ruthenium compound of the porous body precursor can be immobilized. When immobilization is carried out by conventional sintering, for example, a high temperature treatment at 200 ° C or higher is performed to excite dehydration condensation of a stanol group 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 catalyzing the above-described dehydration condensation reaction, the substrate is not damaged, and the substrate can be low before and after 100 ° C. The hot air drying temperature and the short processing time of only a few minutes are wet-processed. Further, after the drying step, ultraviolet irradiation may be performed, and the bonding reaction may be carried out by a photocatalytic reaction in a short-time dry treatment to continuously form a void structure and fix it. The wet treatment initiates the crosslinking reaction while forming the aforementioned coating film, and therefore has the advantage that it can be processed only by the hot air drying step, but also because it is formed empty The gap structure simultaneously initiates a crosslinking reaction and has the disadvantage of hindering the formation of a high void ratio. Further, even if the void structure is formed first and then immersed in the catalyst solution to initiate the bonding reaction, the same phenomenon is expected. In contrast, the dry treatment has a two-stage reaction of initiating a crosslinking reaction after forming a high void structure of a stanol precursor, and thus has an advantage that it is difficult to hinder the formation of a high void structure. Therefore, wet treatment and dry treatment should be used separately for the purpose.

The method of chemically bonding is not particularly limited, and for example, it can be appropriately determined depending on the type of the gelatinous quinone compound. In a specific example, the chemical bonding can be carried out by chemical crosslinking of the fine pore particles of the ruthenium compound, for example, by adding inorganic particles such as titanium oxide to the fine pore particles of the ruthenium compound. Next, the inorganic particles and the fine pore particles of the above ruthenium compound may be chemically crosslinked. 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 can be applied not only to the void layer (polyphosphorus oxide porous body) in which the sol particles are formed to each other, but also to the organic-inorganic hybrid void layer, the host-guest void layer, etc., but not to be such. limited.

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 type of the fine pore particles of the above-mentioned cerium compound. The chemical reaction of the present invention preferably utilizes a dehydration condensation reaction of residual stanol groups 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. However, it is also possible to use a ruthenium monomer material in which other reactive functional groups have been organically modified as a raw material for the cerium oxide gel, in the bonding step. The functional group of the reaction is not limited to only a stanol group. 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, a photobase generating catalyst, a photoacid generator, a photobase generator, and the like which exhibit photocatalytic activity by irradiation with light (for example, ultraviolet rays) are also suitably used. The photoacid generation catalyst, the photobase generating catalyst, the photoacid generator, and the photobase generator are not particularly limited as described above. The above-mentioned catalyst is preferably used in the sol particle liquid containing the pulverized material before being coated, or preferably as a mixed liquid in which the above-mentioned 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 as described above, and examples thereof include various organic solvents, water, and buffer solutions.

The chemical reaction in the presence of the catalyst may be carried out by, for example, irradiating or heating the coating film containing the catalyst previously added to the sol particle liquid; or spraying the coating film. Light irradiation or heating is carried out after the above-mentioned catalyst is attached; or light irradiation or heating is performed while spraying the aforementioned catalyst. For example, when the catalyst is a photoactive catalyst, the microporous particles can be chemically bonded to each other by light irradiation to form the porous body. Further, when the catalyst is a thermally active catalyst, the microporous particles are chemically bonded to each other by heating to form the porous body. The cumulative light amount (energy) of the light irradiation is not particularly limited, and is, for example, 200 to 800 mJ/cm ² , 250 to 600 mJ/cm ² or 300 to 400 mJ/cm ² in terms of @360 nm. In order to prevent the decomposition of light absorption by the catalyst generating agent from progressing due to insufficient irradiation amount, the effect is not satisfactory, and the cumulative light amount of 200 mJ/cm ² or more is preferable. Further, it is preferable to use a cumulative amount of light of 800 mJ/cm ² or less from the viewpoint of preventing the substrate under the void layer from being damaged by thermal wrinkles. 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, as the solvent which can be used, for example, 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, a solvent having a low surface tension is preferred. For example, a lower alcohol represented by isopropyl alcohol (IPA), hexane, perfluorohexane or the like can be used, but it is not limited thereto.

The void structure film of the present invention can be produced in the above manner, but the production method of the present invention is not limited thereto.

In addition, the obtained void structure film of the present invention may be subjected to a treatment such as heating and aging to increase the strength (hereinafter sometimes referred to as "curing step"). For example, in the case where the void structure film 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 time of the aforementioned reaction is, for example, 5 to 30 hr, 7 to 25 hr, or 10 to 20 hr. In the aging step, for example, by setting the heating temperature to a low temperature, it is possible to suppress the shrinkage of the porous polysiloxane porous body and to improve the adhesion peeling strength, thereby achieving both high void ratio and strength.

The phenomenon and mechanism of germination in the strength-increasing step (aging step) are not known, and it is considered that the microporous particles are chemically bonded to each other (for example, by crosslinking reaction) by, for example, a catalyst contained in the void structure film of the present invention. ) Further development to increase strength. In a specific example, when the fine pore particles are fine pore particles of a ruthenium compound (for example, a pulverized body of a gel-like ruthenium dioxide compound) and a residual stanol group (OH group) is present in the polysiloxane porous body, The aforementioned residual stanol groups are chemically bonded to each other by a crosslinking reaction. Further, the catalyst contained in the void structure film of the present invention is not particularly limited, and may be, for example, a catalyst used in the above-mentioned bonding step, or may be a photobase generating catalyst used in the above-mentioned bonding step by light irradiation. The alkaline substance to be produced may be an acidic substance produced by light irradiation of a photoacid generating catalyst used in the above-mentioned bonding step, or the like. However, this description is by way of example and does not limit the invention.

Further, an adhesive layer (adhesive layer forming step) may be further formed on the void structure film of the present invention. Specifically, for example, the above-mentioned adhesive layer may be formed by coating (coating) an adhesive or an adhesive on the porous polysiloxane porous body of the present invention. Further, the adhesive layer side of the adhesive tape or the like in which the adhesive layer is laminated on the substrate may be bonded to the porous polysiloxane porous body of the present invention, thereby forming on the polysiloxane porous body of the present invention. The aforementioned adhesive layer. In this case, the base material such as the adhesive tape may be directly adhered to the bonded state, or may be peeled off from the adhesive layer. In the present invention, the "adhesive" and the "adhesive layer" mean, for example, an agent or a layer which is premised on the re-peeling 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 premised on the adherend. However, in the present invention, "sticky "Ingredients" and "adhesives" are not clearly distinguishable, and "adhesive layer" and "adhesive layer" are not 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, vinyl alcohol, polyoxymethylene, polyester, polyurethane, or 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 of plural types (for example, mixing, lamination, 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 void structure film of the present invention may be reacted with the adhesive layer to form an intermediate layer (intermediate layer forming step) disposed between the void structure film of the present invention and the adhesive layer. By the intermediate layer, for example, the void structure film of the present invention can be prevented from being peeled off from the above-mentioned adhesive layer. 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 embedded in the inside of the void layer in the vicinity of the interface between the void layer and the intermediate layer, so that the interface is firmly fixed (effect). 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, the catalyst used in the foregoing bonding step may be used. Or the alkaline substance generated by the photo-base generating catalyst used in the above-mentioned bonding step by light irradiation, or the acidity generated by the photo-acid generating catalyst used in the above-mentioned bonding step by light irradiation may be used. Substance and so on. Further, the reaction of the void structure film of the present invention with the above-mentioned adhesive layer may be, for example, a reaction (for example, a crosslinking reaction) in which a new chemical bond can be formed. The temperature of the above reaction is, for example, 40 to 80 ° C, 50 to 70 ° C, and 55 to 65 ° C. The time of the aforementioned reaction is, for example, 5 to 30 hr, 7 to 25 hr, or 10 to 20 hr. Further, the intermediate layer forming step may also serve to enhance the strength increasing step (aging step) of the strength of the polysiloxane porous body of the present invention.

The void structure film of the present invention obtained in the above manner can be further laminated with another film (layer) to form a laminated structure containing the porous structure. In this case, in the laminated structure, each constituent element may be laminated by, for example, an adhesive or an adhesive.

The laminate of the above-described respective constituent elements can be laminated by, for example, a continuous treatment using a long film (so-called roll to roll), and the like, when the substrate is a molded article, a component, or the like, After batch processing, the layers are stacked.

Hereinafter, a continuous processing step will be exemplified using FIGS. 1 to 3 for the method of forming the above-described void structure film of the present invention on a substrate. In addition, in the description of the use of the first to third and the following FIGS. 6 to 8 and 9 to 11, the case where the void structure thin film is a polysiloxane porous body will be described as an example. However, when the void structure film of the present invention is a material other than the polysiloxane porous body, it can be produced in the same manner by a continuous treatment step. Further, FIG. 2 shows a step of laminating the protective film and winding it after the porous polysiloxane body is produced. When the other functional film is laminated, the above method may be used, or after the other functional film is coated and dried, the film-forming porous polysiloxane body may be 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 these.

An example of the procedure of the method of forming the above-mentioned polyfluorinated porous body on the substrate is schematically shown in the cross-sectional view of Fig. 1. In Fig. 1, the method for forming a porous polysiloxane porous body comprises: a coating step (1) of applying a sol particle liquid 20" of fine pore particles of a cerium compound to a substrate 10; and a coating film forming step ( a drying step) (2), wherein the sol particle liquid 20" is dried to form a coating film 20", the coating film 20' is the precursor layer of the polyfluorene oxide body; and a chemical treatment step (for example, a crosslinking treatment step) (3) The chemical treatment (for example, cross-linking treatment) of the coating film 20' is performed to form the porous polysiloxane porous body 20. In this manner, 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 sol particle liquid 20" is not particularly limited, and a general coating method may be employed. The coating method may be, for example, a slot die method. Reverse gravure coat method, micro gravure method (micro gravure coat method), 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, based on productivity, smoothness of coating film From the viewpoints of the extrusion coating method, the curtain coating method, the roll coating method, the micro gravure coating method, etc., the aforementioned sol particle liquid The coating amount of the 20" is not particularly limited. For example, the porous structure (polyphosphorus porous body) 20 can be appropriately set to have a suitable thickness. The thickness of the porous structure (polyphosphorus porous body) 20 is not particularly limited. Limited, as described above.

In the drying step (2), the sol particle liquid 20" is dried (i.e., the dispersion medium contained in the sol particle 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), the coating film 20' containing the catalyst (for example, a photoactive catalyst or a thermally active catalyst such as KOH) added before the coating is irradiated or heated by light, The pulverized material in the coating film (precursor) 20' is chemically bonded to each other (for example, crosslinked) to form a polysiloxane porous body 20. The light irradiation or heating conditions of the chemical treatment step (3) are not particularly limited as described above.

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

As shown, each step of the method using the apparatus is carried out while the substrate 10 is being conveyed in one direction by a roll member. The transport 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 transfer roller 101 is carried out while the substrate 10 is unscrewed, and after the coating roller 102 performs the coating step (1) of coating the sol particle liquid 20 on the substrate 10, it is then in the oven zone 110. Move to the drying step (2). In the coating device of Figure 2, the pre-drying step is performed before the drying step (2) after the coating step (1). The pre-drying step may be performed without heating, at room temperature. get on. 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, light is irradiated with a lamp (light irradiation 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 heater (heating means) is used instead of the lamp (light irradiation means) 121 to arrange the substrate 10 on the upper and lower sides of the substrate 10 heating. By this crosslinking treatment, chemical bonding of the above-mentioned pulverized materials in the coating film 20' can be initiated, and the polysiloxane porous body 20 can be hardened and strengthened. In addition, it is also suitable to use an ultraviolet illuminator instead of the air blaster. Then, after the chemical treatment step (3), the laminate of the porous polysiloxane porous body 20 is wound up on the substrate 10 by the take-up roll 105. Further, in Fig. 2, the polycrystalline porous oxygen body 20 of the above-mentioned laminated body is covered and protected by a protective sheet which is unwound by the roller member 106. Here, other laminated layers formed of a long film may be laminated on the porous structure 20 instead of the protective sheet.

Fig. 3 is a view schematically showing an example of a coating apparatus for a micro gravure method (microgravure coating method) and a method for forming the above porous structure using the same. In addition, although the same figure is a cross-sectional view, hatching is omitted for ease of reading.

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

First, the coating step (1) of applying the sol particle liquid 20" to the substrate 10 is carried out while the substrate 10 is unscrewed from the delivery roller 201. The coating of the sol particle liquid 20" is as shown in the drawing. This is carried out using a reservoir area 202, a doctor knife 203, and a micro gravure 204. Specifically, the sol particle 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 applied to the surface of the substrate 10 by the micro gravure 204. 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 sol particle liquid 20" is transported in the oven zone 210 and heated by the heating mechanism 211 in the oven zone 210. The heating mechanism 211 can be, for example, the same as in FIG. Moreover, 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 is 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 dried coating film 20' contains a photoactive catalyst, it is disposed above and below the substrate 10. The lamp (light irradiation means) 221 performs light irradiation. Alternatively, for example, when the coated film 20' after drying contains a thermally active catalyst, a heater (heating means) is used instead of the lamp (light irradiation means) 221 to configure The substrate 10 is heated by a hot air heater (heating mechanism) 221 under the substrate 10. By the crosslinking treatment, the chemical combination of the pulverized materials in the coating film 20' can be excited to form the polysiloxane porous body 20 .

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

Further, another example of the continuous processing step of the method of forming the porous polysiloxane porous body of the present invention is shown in Figs. As shown in the cross-sectional view of FIG. 6, the method is performed after the chemical treatment step (for example, the crosslinking treatment step) (3) of forming the polysiloxane porous body 20, and then the strength upgrading step (aging step) (4) is performed. The methods shown in Figures 1~3 are the same. As shown in Fig. 6, in the strength increasing step (aging step) (4), the strength of the polysiloxane porous body 20 is increased to produce a strength-enhanced polysiloxane porous body 21. The strength increasing step (aging step) (4) is not particularly limited as described in the introduction.

Fig. 7 is a schematic view showing another example of a coating apparatus different from the slit type die coating method of Fig. 2 and a method of forming the above-mentioned polyfluorinated porous body using the same. As shown, the coating device is followed by a chemical treatment zone 120 of the chemical treatment step (3) followed by a strength enhancement zone (maturing zone) 130 for performing a strength enhancement step (aging step) (4), in addition to The device of Figure 2 is identical. 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 enhance the adhesion peel strength of the polysiloxane porous body 20 with respect to the resin film 10, and A polysiloxane porous body 21 having an enhanced adhesion peeling strength is formed. The strength increasing step (aging step) (4) can be carried out by heating the polysiloxane porous body 20 in the above-described manner using a hot air heater (heating means) 131 disposed above and below the substrate 10. The heating temperature, time, and the like are not particularly limited as described in the introduction. Thereafter, in the same manner as in Fig. 3, a laminate of the porous polysiloxane porous body 21 formed on the substrate 10 is taken up by the take-up roll 105. film.

Fig. 8 is a schematic view showing another example of a coating apparatus different from the micro-gravure method (microgravure coating method) of Fig. 3 and a method of forming the above-described porous structure using the same. As shown, the coating device is followed by a chemical treatment zone 220 of the chemical treatment step (3) followed by a strength enhancement zone (maturing zone) 230 for performing a strength enhancement step (aging step) (4), in addition to The device of Figure 3 is the same. That is, after the chemical treatment step (3), a strength-increasing step (aging step) (4) is performed in the strength-enhancing region (aging zone) 230 to enhance the adhesion peeling strength of the polysiloxane porous body 20 with respect to the resin film 10, and A polysiloxane porous body 21 having an enhanced adhesion peeling strength is formed. The strength increasing step (aging step) (4) can be carried out by heating the polysiloxane porous body 20 in the above-described manner by using a hot air heater (heating means) 231 disposed above and below the substrate 10. The heating temperature, time, and the like are not particularly limited as described in the introduction. 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, another example of the continuous processing step of the method of forming the porous polysiloxane porous body of the present invention is shown in Figs. As shown in the cross-sectional view of FIG. 9, the method is included after the chemical treatment step (for example, the crosslinking treatment step) (3) of forming the polysiloxane porous body 20; and the adhesive layer 30 is coated on the polysiloxane porous body 20. The adhesive layer coating step (adhesive layer formation step) (4), and the intermediate layer forming step (5) of reacting the polysiloxane porous body 20 with the adhesive layer 30 to form the intermediate layer 22. In addition to these, the methods of Figures 9-11 are the same as those shown in Figures 6-8. Further, in Fig. 9, the intermediate layer forming step (5) also serves as a step of increasing the strength of the polysiloxane porous body 20 (strength enhancing step) in the intermediate layer shape. After the step (5), the polysiloxane porous body 20 is promoted to be a strength-enhanced polysiloxane porous body 21. However, the present invention is not limited thereto, and for example, the polysiloxane porous body 20 may not be changed 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 as described in the introduction.

Fig. 10 is a schematic view showing still another example of a coating apparatus of a slit type die coating method and a method of forming the above-mentioned polyfluorinated porous body using the same. 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 the adhesive layer coating step (4), and FIG. 7 The device is the same. In the same figure, the intermediate layer forming region (curing zone) 130 disposed immediately behind the adhesive layer coating region 130a can be made to have the strength with FIG. 7 by a hot air heater (heating mechanism) 131 disposed above and below the substrate 10. The lifting zone (maturation zone) 130 is subjected to the same heat treatment. That is, in the apparatus of FIG. 10, 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, it is also possible to have a bonding (attaching) of an adhesive tape or the like of the adhesive layer 30 instead of applying (coating) an adhesive or an adhesive. Then, an intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming region (curing 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 the strength-enhanced polysiloxane porous body 21. The heating temperature, time, and the like by the hot air heater (heating means) 131 are not particularly limited, as in the preface Said.

Fig. 11 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 foregoing porous structure using the same. 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 the adhesive layer coating step (4), and FIG. 8 The device is the same. In the same figure, the intermediate layer forming region (curing zone) 230 disposed immediately behind the adhesive layer coating region 230a can be made to have the strength with FIG. 8 by a hot air heater (heating mechanism) 231 disposed above and below the substrate 10. The lifting zone (maturing zone) 230 is subjected to the same heat treatment. That is, in the apparatus of Fig. 11, after the chemical treatment step (3), an adhesive layer coating step (adhesion layer formation step) (4) is performed, that is, by adhering the layer in the adhesion layer coating region 230a. The 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, it is also possible to have a bonding (attaching) of an adhesive tape or the like of the adhesive layer 30 instead of applying (coating) an adhesive or an adhesive. Then, an intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming region (curing zone) 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 the strength-enhanced polysiloxane porous body 21. The heating temperature, time, and the like by the air heater (heating means) 231 are not particularly limited as described in the introduction.

[3. Use of void structure film]

The void structure film of the present invention can exhibit the same function as the air layer as described above, and therefore can be used in place of the air layer described above. On the object of the air layer. In the present invention, it is characterized by containing the above-mentioned void structure film of the present invention, and other constitutions are not subject to any limitation.

In the present invention, an optical member such as a heat insulating material, a sound absorbing material, a dew condensation preventing material, a low refractive index layer or the like containing the void structure film may be cited. When the members of the present invention are transparent, they can be disposed, for example, at a portion where an air layer is required. The form of the members is not particularly limited and may be, for example, a film.

Moreover, the present invention may be a substrate for regenerative medical treatment characterized by containing the void structure film. The aforementioned substrate is, for example, a scaffold material. As described above, the void structure film of the present invention has a porous structure which exhibits the same function as the air layer. The voids of the void structure film are suitable, for example, for holding cells, nutrient sources, air, etc., and therefore the void structure film of the present invention can be effectively used as a stent for regenerative medicine, for example.

The member containing the void structure film of the present invention may be, for example, a total reflection member, an ink image receiving material, a single layer AR (anti-reflection), a single layer moth eye, or a dielectric constant material in addition to the above. Wait.

Example

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

(Example 1)

In the present embodiment, the porous structure of the present invention is produced in the following manner.

(1) Gelation of bismuth compounds

The ruthenium compound precursor MTMS 0.95g was dissolved in 2.2 g of DMSO. 0.5 g of a 0.01 mol/L aqueous oxalic acid solution was added to the above mixture, and the mixture was stirred at room temperature for 30 minutes to hydrolyze MTMS to form hydroxymethyl decane.

After adding 0.38 g of 28% aqueous ammonia and 0.2 g of pure water to 5.5 g of DMSO, the above-mentioned hydrolyzed mixture was further added thereto, and stirred at room temperature for 15 minutes to carry out coagulation of hydroxymethyl decane. Gelatinized to obtain a gelatinous quinone compound.

(2) ripening treatment

The gelled mixture was directly incubated at 40 ° C for 20 hours to carry out a ripening treatment.

(3) crushing treatment

Next, the gelled cerium compound which has been subjected to the aging treatment is pulverized into pellets having a size of several mm to several cm using a spatula. 40 g of IPA was added thereto, and after stirring for a while, it was allowed to stand at room temperature for 6 hours, and the solvent and the catalyst in the gel were decanted. After the same decantation treatment was repeated 3 times, the solvent substitution was terminated. Then, the aforementioned gelatinous cerium compound in the above mixture is subjected to high-pressure medium-free pulverization. In the pulverization treatment, a homogenizer (trade name: UH-50, manufactured by SMT Co., Ltd.) was used, and 1.18 g of gel and 1.14 g of IPA were weighed in a 5 cc spiral bottle, and then pulverized at 50 W and 20 kHz for 2 minutes.

After the gelatinous ruthenium compound in the mixed liquid is pulverized by the pulverization treatment, the mixed liquid is a sol particle liquid of the pulverized product. The volume average particle diameter was 0.50 to 0.70 as determined by a dynamic light scattering type Nanotrac particle size analyzer (manufactured by Nikkiso Co., Ltd., UPA-EX150 type), and the volume average particle diameter indicates the pulverized material contained in the mixed liquid. Particle size deviation. Prepare a 0.3% by weight aqueous solution of KOH, before 0.5 g of the sol particle liquid was added to 0.02 g of catalyst KOH to prepare a coating liquid.

(4) forming a coating film and forming a polysilicon porous body

Next, the coating liquid was applied onto the surface of a polyethylene terephthalate (PET) substrate by a bar coating method to form a coating film. The coating system was prepared by using 6 μL of the sol particle liquid per 1 mm ^{2 of the} surface of the substrate. After the coating film was treated at a temperature of 100 ° C for 1 minute, the crosslinking reaction of the pulverized materials was completed. Thereby, a porous polysiloxane body having a thickness of 1 μm in which the pulverized materials were chemically bonded to each other was formed on the substrate. Thus, a void structure film is produced.

(Comparative Example 1)

A porous body was formed in the same manner as in Example 1 except that the catalyst KOH was not added to the coating liquid.

(5) Confirmation of the characteristics of the porous structure

The porous body was peeled off from the substrate, and the strength (scratch resistance obtained by Bemcot (registered trademark)) was confirmed by the above method. The refractive index, haze and void ratio were also measured.

These results are shown in Table 1 below.

As shown in Table 1 above, the polymerization of Example 1 having a thickness of 1 μm was obtained. The porous oxygen-containing porous body has a porous structure having a high void ratio, and it has been confirmed that it has both sufficient strength and flexibility. Therefore, it is understood that the porous polysiloxane porous body of the present invention is useful as a porous stanol which can have both film strength and flexibility by crosslinking the cooked cerium oxide compound sol. Further, the porous tantalum porous body of Example 1 also had good optical characteristics of low refractive index and low haze. Further, a cross-sectional SEM image of the porous polysiloxane porous body of Example 1 is shown in Fig. 4 . Further, a TEM image of fine pore particles of the porous polysiloxane porous body of Example 1 is shown in Fig. 5 .

(Example 2)

In the present embodiment, the void structure film (polyoxynitride porous body) of the present invention is produced in the following manner.

First, the above "(1) gelation of bismuth compound" and "(2) aging treatment" were carried out in the same manner as in Example 1. Then, an IPA (isopropyl alcohol) solution of a catalyst (manufactured by Wako Pure Chemical Industries, Ltd.: trade name: WPBG266) was added to the sol particle liquid in an amount of 1.5% by weight to replace the 0.3% by weight aqueous KOH solution. The above "(3) pulverization treatment" was carried out in the same manner as in Example 1 to prepare a coating liquid. The amount of the IPA solution of the photobase generating catalyst was set to 0.031 g with respect to 0.75 g of the sol particle liquid. Then, the above "(4) formation of a coating film and formation of a porous polysiloxane body" was carried out in the same manner as in Example 1. The dried porous body obtained in the above manner was irradiated with UV. The irradiation of UV light irradiated light having a wavelength of 360 nm, and the amount of light irradiation (energy) was 500 mJ. Thereafter, after UV irradiation, the film was heated and aged at 60 ° C for 22 hours to form a porous structure of the present example.

(Example 3)

The porous structure of this example was formed in the same manner as in Example 2 except that the heating and aging were not carried out after the irradiation of UV.

(Example 4)

After the addition of the photobase to the IPA solution of the catalyst, the same operation as in Example 2 was carried out, except that 0.018 g of 5% by weight of bis(trimethoxy)decane was added to 0.75 g of the sol solution to adjust the coating liquid. The porous structure of this example was formed.

(Example 5)

The porous structure of this example was formed in the same manner as in Example 2 except that the amount of the IPA solution of the photobase generating catalyst was changed to 0.74 g.

(Example 6)

After the dried porous body was irradiated with UV in the same manner as in Example 2, the adhesive side of the PET film coated with the adhesive (adhesive layer) on one side was attached to the adhesive side at room temperature before the heating and aging. After the porous body described above, it was aged by heating at 60 ° C for 22 hr. Except for this, the same operation as in Example 2 was carried out to form a porous structure of the present example.

(Example 7)

The porous structure of this example was formed in the same manner as in Example 6 except that the PET film was not attached and then heated and aged.

(Example 8)

After adding the photobase to the IPA solution of the catalyst, 0.718 g of 5% by weight of bis(trimethoxy)decane was added to the above sol solution to adjust the coating. The same operation as in Example 6 was carried out, except that the liquid was used to form the porous structure of the present Example.

(Example 9)

The porous structure of this example was formed in the same manner as in Example 6 except that the amount of the IPA solution of the photobase generating catalyst was changed to 0.74 g.

(Embodiment 10)

The porous structure of this example was formed in the same manner as in Example 6 except that MgF ₂ and TEOS (tetraethoxyoxane) were mixed in place of MTMS to form a porous structure.

With respect to the porous structures of Examples 2 to 10, the refractive index and haze were measured by the above methods, and the results are shown in Tables 2 and 3 below.

As shown in the above Tables 2 and 3, in the polyaluminum oxide porous bodies of Examples 2 to 10 which were obtained to have a thickness of 1 μm, the refractive index was extremely low at 1.14 to 1.18, and fog. The value also shows an extremely low value of 0.4 with excellent optical properties. Further, the state in which the refractive index is extremely low as described above indicates that the void ratio is high. Further, actually, as shown in Tables 2 and 3, it was confirmed that the void ratio was relatively high. Further, it was also confirmed that the porous polysiloxane bodies of Examples 2 to 10 had sufficient strength and flexibility as in Example 1. Further, in Examples 2 to 10, after the coating liquid was stored for one week, no change was observed by visual observation, and it was confirmed that the coating liquid was also excellent in storage stability, and it was possible to efficiently produce a stable quality polysiloxane porous body. .

Industrial availability

As described above, the void structure film of the present invention is characterized in that one or more constituent units capable of forming a fine void structure are chemically bonded to each other via a catalytic action, and for example, the porous polysiloxane porous body of the present invention contains the aforementioned pulverization of the gelatinous ruthenium compound. The porous structure having a void is formed, and the pulverized material is chemically bonded by the porous structure to fix the porous structure. Therefore, the void structure film of the present invention has a structure having a void and can maintain sufficient strength and flexibility. Therefore, the void structure film of the present invention can effectively provide a void structure which requires film strength and flexibility. For example, it can be applied to a wide range of articles as a member using voids, such as an optical member such as a low refractive index layer, a heat insulating material or a sound absorbing material, an ink image receiving material, or the like.

Claims (22)

A void structure film characterized in that one or more constituent units capable of forming a fine void structure are chemically bonded to each other via a catalytic action. The void structure film of claim 1, wherein the aforementioned constituent units contain a direct bond with each other. The void structure film of claim 1 or 2, wherein the aforementioned constituent units have an indirect bond with each other. The void structure film of claim 1 or 2, wherein the combination of the aforementioned constituent units includes a hydrogen bond or a covalent bond. The void structure film according to claim 1 or 2, wherein the constituent unit is selected from the group consisting of at least one of a group consisting of a particle shape, a fiber shape, and a flat shape. The void structure film of claim 5, wherein the particulate and flat constituent unit is composed of an inorganic material. The void structure film according to claim 5, wherein the constituent element of the particulate constituent unit contains at least one element selected from the group consisting of Si, Mg, Al, Ti, Zn, and Zr. The void structure film according to claim 5, wherein the particulate constituent unit contains fine pore particles of a ruthenium compound. The void structure film of claim 8, wherein the fine pore particles comprise a pulverized body of a gelatinous cerium oxide compound. The void structure film of claim 9, wherein the pulverized body of the gelled cerium oxide compound is deposited on a substrate to form a film. The void structure film of claim 10, wherein the film formed of the foregoing cerium oxide compound exhibits a scratch resistance of 60 to 100% by using Bemcot, and exhibits flexibility of the MIT test. The number of times is more than 100 times. The void structure film of claim 1 or 2 further comprising a crosslinking auxiliary agent for indirectly bonding the aforementioned constituent units to each other. The void structure film of claim 12, wherein the content of the crosslinking auxiliary agent is 0.01 to 20% by weight based on the weight of the constituent unit. A method for producing a void structure film according to any one of claims 8 to 13, characterized by comprising the steps of: preparing a liquid containing fine pore particles of a cerium compound; and adding the fine pore particles of the cerium compound to the liquid a catalyst chemically bonded to each other; and a bonding step of chemically bonding the aforementioned microporous particles to each other by a catalytic action. The method for producing a void structure film according to claim 14, wherein the catalyst reaction in the aforementioned bonding step is a wet treatment and/or a dry treatment. The method for producing a void structure film according to claim 14 or 15, wherein the fine pore particles of the cerium compound contain cerium oxide sol fine particles. The method for producing a void structure film according to claim 16, wherein the cerium oxide sol fine particle system is obtained by pulverizing a gelled cerium oxide compound. The method for producing a void structure film according to claim 17, wherein the powder The broken system is carried out by high-pressure medium-free pulverization. The method of producing a void structure film according to claim 14 or 15, wherein in the aforementioned bonding step, the aforementioned chemical bond is a cross-linking bond. The method for producing a void structure film according to claim 14 or 15, wherein the drying temperature at which the catalyst reaction is carried out in the aforementioned bonding step is 50 ° C or more and less than 200 ° C. The method for producing a void structure film according to claim 14 or 15, further comprising the step of adding a crosslinking auxiliary agent to the liquid, the crosslinking auxiliary agent for indirectly bonding the microporous particles of the foregoing cerium compound to each other. The method for producing a void structure film according to claim 21, wherein the crosslinking auxiliary agent is added in an amount of from 0.01 to 20% by weight based on the weight of the fine pore particles of the cerium compound.