TW201631071A - Coating material and method for manufacturing same - Google Patents

Abstract

The purpose of the present invention is to provide a coating material capable of forming a void structure having strength and flexibility. This coating material is characterized by including a dispersion medium and a crushed product of a gelled silicon compound obtained from a silicon compound including at least a trifunctional or lower saturated-bonded functional group, the crushed product containing a residual silanol group. This method for manufacturing a coating material is characterized by including, for example, a step for mixing a dispersion medium and a gelled silicon compound obtained by gelling a silicon compound including at least a trifunctional or lower saturated-bonded functional group. Through use of this coating material, a porous structure can be formed by applying the coating material on a substrate, forming a coating film, and chemically bonding together the crushed product included in the coating film.

Description

Paint and its manufacturing method Field of invention

The present invention relates to a coating and a method of making the same.

Background of the invention

A sol liquid for a porous liquid of stanol which can form a void structure using a silica compound material (a ruthenium compound material) as a raw material has been discussed variously. The common point is that after the gelation of the oxygen-containing compound, the pulverized sol liquid obtained by pulverizing the gelled oxime compound is prepared and applied to form a void structure. However, in order to obtain a high porosity, there is a problem that the film strength of the porous stanol is remarkably lowered, and it is difficult to industrially produce a porous stanol. An example in which the high porosity and the strength are applied to the antireflection layer is described (for example, refer to Patent Documents 1 to 4). In this method, after forming a void layer on a lens, it is fired at a high temperature of 150 ° C or higher for a long time, but the gel using TEOS is poor in flexibility, so it is not flexible. A problem of forming a porous body on a substrate. In addition, there is an application example of the void layer which is not subjected to the baking treatment (see, for example, Non-Patent Document 1). However, in this method, the stanol-molded sol contains a large amount of residual stanol groups and is not subjected to a calcination treatment after the formation of the void layer. Therefore, the obtained porous body has poor film strength and cannot be imparted. The problem of resistance to scratching.

In order to solve these problems, an attempt has been made to develop a film which can be used in place of an air layer formed by voids between members.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2006-297329

Patent Document 2: Japanese Patent Laid-Open Publication No. 2006-221144

Patent Document 3: Japanese Patent Laid-Open No. 2006-011175

Patent Document 4: Japanese Patent Laid-Open Publication No. 2008-040171

Non-patent literature

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

Summary of invention

In the past, it has never been reported that a sol coating which can obtain a void layer which can easily achieve both film strength and flexibility can be obtained. Accordingly, an object of the present invention is to provide a stanol sol coating which can be easily formed into a void layer having a high porosity (void ratio), film strength and flexibility, for example, by continuous treatment.

In order to achieve the above object, the polyphosphonium oxysol coating of the present invention is characterized by comprising a pulverized material of a gelatinous cerium compound and a dispersion medium, and the gel-like cerium compound is composed of a saturated bond functional group containing at least 3 functional groups or less. The ruthenium compound is prepared; the pulverized material contains more than 1 mol% of residual ruthenium An alkanol group, and the aforementioned polyphosphonium oxysol coating is a coating for chemically bonding the aforementioned pulverized materials to each other.

The method for producing a polyfluorene oxysol coating material of the present invention comprises the step of mixing a pulverized material of a gelatinous cerium compound with a dispersion medium, and the gelatinous cerium compound is composed of a saturated bond functional group containing at least 3 functional groups A base compound is prepared.

The first coating material of the present invention is characterized in that it contains a gelatinous quinone compound and is used as a raw material for producing the polyfluorene oxysol coating material of the present invention, and the gelatinous quinone compound is saturated with at least trifunctional or less. A bond-functional oxime compound is prepared.

The method for producing a first coating material of the present invention is characterized by comprising a gelation step of gelling a ruthenium compound containing at least a trifunctional or less saturated bond functional group in a solvent to form a gelatinous ruthenium compound.

The second coating material of the present invention is characterized by comprising a gel-like cerium compound and a raw material for producing the polyfluorene oxysol coating material of the present invention, wherein the gel-like cerium compound contains at least a trifunctional or less saturated bond. The gelatinous substance obtained from the functional oxime compound is subjected to a ripening treatment.

The method for producing a second coating material according to the present invention is characterized in that it comprises a ripening step of aging a gelatinous quinone compound in a solvent, and the gelatinous quinone compound is a hydrazine having at least a trifunctional or less saturated functional group. Made from the compound.

The polydecane oxysol coating material of the present invention contains the pulverized material of the above gelled cerium compound, and the pulverized materials can be chemically bonded to each other. therefore, For example, in the coating film using the above-mentioned coating material, a porous polysiloxane porous body having voids can be produced by chemically bonding the above-mentioned pulverized materials to each other.

As a result of intensive studies by the present inventors, it has been found that the gel-like stanol compound can be chemically bonded to each other by leaving the stanol group remaining. Further, it has been found that the polyfluorene oxide sol coating according to the present invention can be easily and easily formed into a polysiloxane porous body by, for example, forming a coating film and chemically bonding the pulverized materials in the coating film to each other. A void layer that combines strength and flexibility. According to the polydecane sol coating of the present invention, for example, the aforementioned stanol porous body can be applied to various objects. Specifically, the polysiloxane porous body obtained by using the polyoxyxide sol paint of the present invention can be used as, for example, a heat insulating material, a sound absorbing material, a scaffold for regenerative medical materials, a dew condensation preventing material, an optical member, or the like, instead of the air layer. Therefore, the polydecane oxysol coating of the present invention and the method for producing the same can effectively produce, for example, a porous polysiloxane body as described above.

10‧‧‧Substrate

20‧‧‧Porous structure

20'‧‧‧ coated film (precursor layer)

20"‧‧‧ paint

21‧‧‧Strengthened porous structure

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 using the coating material of the present invention.

Fig. 2 is a view schematically showing a part of a step of producing a porous polysiloxane porous body using the coating material of the present invention and an example of a device used therefor.

Fig. 3 is a view schematically showing a part of the steps of producing a polysiloxane porous body using the coating material of the present invention and another example of the apparatus used therein.

Figure 4 is a cross-sectional view showing a further example of a method of forming a porous polysiloxane body on a substrate in the present invention.

Figure 5 is a schematic view showing the use of the coating of the present invention to produce polysilicon porous A part of the steps of the body and a diagram of another example of the device used.

Fig. 6 is a view schematically showing a part of the steps of producing a polysiloxane porous body using the coating material of the present invention and another example of the apparatus employed.

Figure 7 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. 8 is a view schematically showing a part of the steps of producing a polyfluorinated porous body using the coating of the present invention and another example of the apparatus employed.

Fig. 9 is a view schematically showing a part of the steps of producing a polysiloxane porous body using the coating material of the present invention and another example of the apparatus employed.

Form for implementing the invention

In the coating material of the present invention, for example, the pulverized material has a volume average particle diameter of 0.05 to 2.00 μm. In the present invention, the shape of the "particles" (for example, particles of the pulverized material, etc.) is not particularly limited, and may be, for example, a spherical shape or an aspherical system. Further, in the present invention, the particles of the pulverized material may be, for example, sol-gel beaded particles, nano particles (hollow nano cerium oxide/nanosphere particles), or nanofibers.

In the coating material of the present invention, for example, the hydrazine compound is a compound represented by the following formula (2).

The coating material of the present invention contains, for example, a catalyst for chemically bonding the pulverized materials to each other.

The method for producing a coating material of the present invention further comprises, for example, a pulverization step of pulverizing the gelatinous cerium compound in a solvent, and the pulverized material obtained by the pulverizing step is used in the mixing step.

The method for producing a coating material of the present invention further comprises, for example, a gelation step of gelling the cerium compound in a solvent to form a gelatinous cerium compound, and using the gel obtained by the above-described production step in the pulverizing step A compound.

The method for producing a coating material of the present invention further includes, for example, a aging step of aging the gelatinous quinone compound in a solvent, and the gelating step is the gelatinous quinone compound after the aging step.

In the method for producing a coating material of the present invention, for example, the gelatinous quinone compound is cultured at a temperature of 30 ° C or higher in the solvent in the ripening step.

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.

[1. Coating and its manufacturing method]

As described above, the polyphosphonium oxysol coating of the present invention is characterized in that it contains a pulverized product of a gelatinous quinone compound and a solvent, and the gelatinous quinone compound is obtained from a hydrazine compound containing at least a functional group having at least 3 functional groups. The pulverized material contains a residual stanol group, and the poly oxime sol coating of the present invention is a coating for chemically bonding the pulverized materials to each other. The "saturated bond functional group having a trifunctional group or less" means that the fluorene compound has three or less functional groups and the functional groups form a saturated bond with cerium (Si).

As described above, the method for producing a coating material of the present invention is the method for producing a polyfluorene oxide sol coating material according to the present invention, which comprises the step of mixing a pulverized material of a gelatinous cerium compound and a dispersion medium, the gelatinous mash The compound is a ruthenium compound containing at least a functional group having at least 3 functional groups Made of things.

The coating material of the present invention can be used to produce a porous polysiloxane body which exhibits the same function as the air layer (for example, low refractive index), as will be described later. Specifically, the coating material obtained by the production method of the present invention contains the pulverized material of the gelatinous cerium compound, and the three-dimensional structure of the pulverized cerium compound which is not pulverized is damaged and formed into the unpulverized A completely new three-dimensional structure of gelatinous bismuth compounds. Therefore, for example, a coating film (polyoxygenated porous body precursor) formed by using the above-mentioned coating material can be a new pore structure (new void structure) which can be formed without forming a layer formed by the aforementioned unpulverized gel-like cerium compound. The layer of). Thereby, the layer can perform the same function as the air layer (for example, the same low refractive index). Further, in the coating material of the present invention, since the pulverized material contains a residual stanol group, the pulverized material can be chemically bonded to each other by forming a completely new three-dimensional structure with the coating film (polyfluorinated porous body precursor). Thereby, the formed polysiloxane porous body has a structure of voids, but maintains sufficient strength and flexibility. Therefore, according to the present invention, the porous polysiloxane porous body can be easily and easily supplied to various objects. The coating material produced by the production method of the present invention is very useful, for example, in the production of the above-described porous structure which can be used as a substitute for the air layer. Further, in the case of the air layer, for example, it is necessary to form a gap by providing a gap between the member and the member, and to form an air layer between the members. However, the porous polysiloxane body formed using the coating material of the present invention only needs to be disposed at the target site, and can exhibit the same function as the above air layer. Therefore, as described above, it is possible to easily and easily impart the same function to the various objects as the air layer as compared with the formation of the air layer. Specifically, the porous structure can be used as a heat insulating material, a sound absorbing material, a stent for regenerative medical treatment, a dew condensation preventing material, or the like, for example, instead of the air layer.

The coating material of the present invention may be, for example, a coating material for forming a polysiloxane porous body or a coating material for forming a low refractive layer. In the coating material of the present invention, the aforementioned gelatinous quinone compound is a pulverized material thereof.

In the porous polysiloxane body of the present invention, the volume average particle diameter of the pulverized material is not particularly limited, and the lower limit thereof is, for example, 0.05 μm or more, 0.10 μm or more, 0.20 μm or more, 0.40 μm or more, and the upper limit thereof is, for example, 2.00 μm or less. 1.50 μm or less and 1.00 μm or less, and the range thereof is, for example, 0.05 μm to 2.00 μm, 0.20 μm to 1.50 μm, and 0.40 μm to 1.00 μm. The aforementioned volume average particle diameter means the particle size deviation of the aforementioned pulverized material in the coating material of the present invention. The particle size distribution can be measured by, for example, a particle size distribution evaluation device such as a dynamic light scattering method or a laser diffraction method, an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

Further, in the coating material of the present invention, the particle size distribution of the pulverized material 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 indicates the particle size deviation of the aforementioned pulverized material in the coating material of the present invention. The aforementioned particle size distribution can be measured, for example, by a particle size distribution evaluation device or an electron microscope.

In the coating material of the present invention, the hydrazine compound is, for example, a compound represented by the following formula (2).

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 above R ² may be, for example, an example of R ¹ of the following formula (1).

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

In the coating material of the present invention, the concentration of the pulverized product of the gelatinous cerium compound in the dispersion medium is not particularly limited, and is, for example, 0.3 to 50% (v/v), 0.5 to 30% (v/v), 1.0~10% (v/v). Once the concentration of the pulverized material is too high, for example, the fluidity of the sol solution may be significantly lowered. Coagulum ‧ smears are produced during coating. On the other hand, if the concentration of the pulverized material is too low, for example, it takes a considerable time for the solvent to dry, and the residual solvent immediately after drying is increased, so that the void ratio may be lowered. Further, the coating material of the present invention is preferably bonded to a helium atom, for example, by a helium atom. In a specific example, the ratio of unbonded ruthenium atoms (that is, residual stanol) among the total ruthenium atoms contained in the coating material is, for example, less than 50%, 30% or less, and 15% or less.

The physical properties of the coating of the present invention are not particularly limited. The shear viscosity of the coating material is, for example, at a shear rate of 10001/s, for example, 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 transfer rate of gravure coating may be lowered. Conversely, once the shear viscosity is too low, for example, it may not be possible to thicken the wet coating thickness at the time of coating and not to obtain a desired thickness after drying.

In the coating material of the present invention, the dispersion medium (hereinafter also referred to as "solvent for coating") is not particularly limited, and examples thereof include a gelling solvent and a solvent for pulverization which will be described later, and the solvent for pulverization is preferable. The solvent solvent for coating may be an organic solvent having a boiling point of 130 ° C or lower. Specific examples thereof include IPA, ethanol, methanol, butanol, and the like.

The coating material of the present invention may further contain, for example, a catalyst for chemically bonding the pulverized materials of the gelatinous cerium compound 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 pulverized product of the gelled cerium compound.

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

The paint of the present invention is, for example, a sol-like pulverized material dispersed in the solvent, and is also referred to as, for example, a "sol particle liquid". The coating of the present invention can be continuously formed into a void layer having a film strength of a certain degree or more, for example, after being applied to a substrate and dried, and then chemically crosslinked by a bonding step. Further, the "sol" of the present invention means that the three-dimensional structure of the gel is pulverized, and the pulverized material (that is, the cerium oxide sol particles having a three-dimensional structure in which a part of the void structure is maintained) is dispersed in a solvent and appears to flow. Sexual state.

Hereinafter, the production method of the present invention will be described, and the paint of the present invention can be used as follows.

In the production method of the present invention, the mixing step is a step of mixing a pulverized product of a gelatinous ruthenium compound and a dispersion medium, and the gel-like ruthenium compound is a functional group having at least a trifunctional or less saturated bond. Made of bismuth compounds. In the present invention, the pulverized product of the gelatinous ruthenium compound can be obtained, for example, from the gelatinous ruthenium compound by a pulverization step described later. Therefore, the gelatinous quinone compound may be referred to as, for example, the first coating material of the coating of the present invention. In addition, the pulverized product of the gelatinous ruthenium compound can be obtained, for example, from the gelatinous ruthenium compound which has been subjected to the ripening step of the aging step described later by a pulverization step which will be described later. Therefore, the aforementioned ripening The gelatinous quinone compound after the treatment may be referred to as, for example, a second coating material of the coating of the present invention.

In the production method of the present invention, the gelation step is a step of gelling a ruthenium compound containing at least a trifunctional or less saturated bond functional group in a solvent to form a gelatinous ruthenium compound (first coating material). The gelation step is, for example, a step of gelling the monomeric ruthenium compound by a dehydration condensation reaction in the presence of a dehydration condensation catalyst, whereby a gelatinous ruthenium compound can be obtained. As described above, the gelatinous quinone compound has a residual stanol group, and the residual stanol group is preferably appropriately adjusted in accordance with chemical bonding between the pulverized materials of the gelatinous quinone compound described later.

In the gelation step, the ruthenium compound is not particularly limited as long as it is gelated by a dehydration condensation reaction. By the above-described dehydration condensation, for example, the above ruthenium compounds can be combined. The combination between the aforementioned hydrazine compounds is, for example, hydrogen bonding or intermolecular force bonding.

The above hydrazine compound can be represented by the following formula (1). Since the oxime compound of the above formula (1) has a hydroxyl group, the ruthenium compound of the above formula (1) can be hydrogen-bonded or intermolecularly bonded, for example, through the respective 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 above hydrazine compound may be, for example, a precursor which forms a hydrazine compound of the above formula (1) by hydrolysis. The precursor may be, for example, any one of the compounds represented by the above formula (2), as long as it can be produced by hydrolysis.

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

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

In the present invention, the hydrazine compound may, for example, be a hydrolyzate of trimethoxy(methyl)decane.

The ruthenium compound of the above monomer is not particularly limited, and for example, it can be suitably selected in accordance with the use for producing a porous siloxane porous body. In the production process of the porous polysiloxane porous body, for example, when low refractive index is emphasized, the ruthenium compound is preferably the above-mentioned trifunctional decane, and the strength is emphasized (for example, from the viewpoint of good low refractive index). In the case of scratch resistance, it is preferable that the ruthenium compound is preferably the above-mentioned tetrafunctional decane based on the scratch resistance. In addition, the above-mentioned hydrazine compound which is a raw material of the above-mentioned gelatinous quinone compound may be used alone or in combination of two or more kinds. In a specific example, the 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 ruthenium compounds. . When two or more kinds of hydrazine compounds are used as the hydrazine compound, the ratio thereof is not particularly limited, and can be appropriately set.

The gelation of the above hydrazine compound can be carried out, for example, by a dehydration condensation reaction between the above hydrazine compounds. The dehydration condensation reaction is preferably carried out, for example, in the presence of a catalyst, and examples of the catalyst include a dehydration condensation catalyst such as an acid catalyst and a basic catalyst, and the acid catalyst includes hydrochloric acid, oxalic acid, sulfuric acid, etc., and the alkaline catalyst. There are ammonia, potassium hydroxide, sodium hydroxide, ammonium hydroxide and the like. The foregoing The dehydration condensation catalyst may be an acid catalyst or may be an alkaline catalyst, and an alkaline catalyst is preferred. In the dehydration condensation reaction, the amount of the catalyst added to the ruthenium compound is not particularly limited. For example, the catalyst is 0.1 to 10 moles, 0.05 to 7 moles, 0.1 to 0.1% of the ruthenium compound. 5 moles.

The gelation of the aforementioned hydrazine compound is preferably carried out, for example, in a solvent. The ratio of the above hydrazine compound in the aforementioned solvent is not particularly limited. The aforementioned solvent may, for example, be dimethyl hydrazine (DMSO), N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc), dimethylformamide (DMF), γ- Butyrolactone (GBL), acetonitrile (MeCN), ethylene glycol ethyl ether (EGEE), and the like. The solvent may be used alone or in combination of two or more. The solvent used for the gelation 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 primary particle of the ruthenium compound can be formed by growing a siloxane bond, and the primary particles can be connected to each other in a bead shape as the reaction progresses to form a three-dimensional gel.

The gel form of the aforementioned gelatinous quinone compound obtained in the gelation step described above is not particularly limited. "Gel" generally refers to a structure in which a solute has a set of kinetics that lose its independence due to interaction, and exhibits a solidified state. In addition, in the gel, the wet gel is generally referred to as a structure containing a dispersion medium and solute in a dispersion medium, and the dry gel means removing the solvent. And the solute adopts a mesh structure having a void. In the present invention, as the gelatinous quinone compound, for example, a wet gel is preferably used. The residual amount of the stanol group of the gelled quinone compound is not particularly limited, and for example, the range described later can be similarly exemplified.

The gelatinous quinone compound obtained by the gelation may be directly supplied to the pulverization step, for example, or may be subjected to a aging treatment in the aging step before the pulverization step. In the above-mentioned ripening step, the conditions of the above-mentioned ripening treatment are not particularly limited, and for example, the gelatinous quinone compound may be cultured at a predetermined temperature in a solvent. By the above-described ripening treatment, for example, the gel-like cerium compound having a three-dimensional structure obtained by gelation can further grow the primary particles, whereby the size of the particles themselves can be increased. Moreover, as a result, the contact state of the neck in which the aforementioned particles are in contact with each other can be expanded, for example, from a point contact to a surface contact. The gelatinous quinone compound which has been subjected to the above-mentioned aging treatment, for example, increases the strength of the gel itself, and as a result, the strength of the three-dimensional basic structure of the pulverized material after pulverization can be further enhanced. Thereby, when the coating film is formed using the coating material of the present invention, for example, even in the drying step after coating, the pore size of the void structure which can suppress the deposition of the three-dimensional basic structure can be suppressed in the aforementioned drying step. The solvent in the coating film volatilizes and shrinks.

The lower limit of the temperature of the ripening treatment is, for example, 30° C. or higher, 35° C. or higher, or 40° C. or higher, and the upper limit thereof is, for example, 80° C. or lower, 75° C. or lower, or 70° C. or lower, and the range is, for example, 30 to 80° C. ~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 optimum conditions for the aging are preferably set such that the size of the primary particles of the gelatinous quinone compound is increased and the contact area of the neck portion is increased. Further, in the above-mentioned ripening step, the temperature of the ripening treatment is preferably such as the boiling point of the solvent to be used. In the aging treatment, for example, when the aging temperature is too high, the solvent may be excessively volatilized, and the pores of the three-dimensional void structure may be closed due to concentration of the coating liquid. On the other hand, in the above-mentioned ripening treatment, for example, when the ripening temperature is too low, not only the above-described ripening effect cannot be sufficiently obtained, but the temperature fluctuation of the mass production process is also increased, and it is possible to produce a product having poor quality.

For the above-mentioned ripening treatment, for example, the same solvent as the gelation step described above can be used, and specifically, the reactant after the gel treatment (that is, the solvent containing the gelatinous ruthenium) is preferably directly carried out. The number of residual stanolol groups contained in the gelatinous quinone compound after the gelation treatment is, for example, an alkane of a raw material (for example, the aforementioned hydrazine compound or a precursor thereof) used in gelation. The lower limit of the ratio of the residual stanol group in the case where the number of oxymoles is 100 is, for example, 1% or less, 3% or less, or 5% or less, and the upper limit thereof is, for example, 50% or more, 40% or more, or 30% or more. The range is, for example, 1 to 50%, 3 to 40%, and 5 to 30%. For the purpose of increasing the hardness of the gelatinous quinone compound, for example, the lower the molar number of the residual stanol group is, the better. When the number of moles of the residual stanol group is too high, for example, in the formation of the aforementioned porous porous body, the void structure may not be maintained until the precursor of the polysiloxane porous body is crosslinked. On the other hand, when the number of moles of the residual stanol group is too low, for example, the aforementioned precursor of the polysiloxane porous body in the aforementioned bonding step Crosslinking may not be possible, and sufficient film strength cannot be imparted. Further, the above-mentioned residual stanol group is exemplified, and when the ruthenium compound is modified as a raw material of the gelatinous ruthenium compound by using various reactive functional groups, the same phenomenon can be applied to each functional group. on.

In the present invention, the aforementioned pulverizing step is as described above for the step of pulverizing the aforementioned gel-like oxime compound. The pulverization can be carried out, for example, on the gelatinous quinone compound (first coating material) after the gelation step, and the gelled bismuth compound (second coating material) after the aging treatment described above can be performed. Implementation.

In the pulverization, for example, the gelatinous ruthenium compound in the solvent for gelation may be directly subjected to pulverization treatment, or the gelation solvent may be changed to another solvent, and then the gelatinous ruthenium compound in the other solvent may be used. The pulverization process is performed. Further, when the above-mentioned aging step is carried out on the gelatinous quinone compound, it is preferably changed to another solvent in the case where, for example, the catalyst and solvent used in the gelation step remain after the aging step, and further Gelation over time affects the pot life of the finally obtained coating, or causes drying efficiency to decrease when dried using the coating film formed by the above coating. The other solvent described above is also referred to as "solvent solvent" hereinafter.

For the pulverization, for example, the same solvent as the gelation step and the aging step described above may be used, and a solvent different from the gelation step and the aging step may be used. In the case of the former, for example, the above-described aging step and the pulverization treatment may be directly performed on the reactant after the gelation step (for example, the gelling solvent containing the gel-like ruthenium compound). In addition, in the latter case, it is possible to reverse the aforementioned gelation step. After the above-mentioned aging step is directly performed on the object (for example, the solvent for gelation containing the gelatinous ruthenium compound), the gelation solvent is changed to another solvent, and then the gelatinous ruthenium compound in the other solvent is added. The pulverization process is performed.

The solvent for pulverization 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 less, a boiling point of 100 ° C or less, and a boiling point of 85 ° C or less. Specific examples thereof include isopropyl alcohol (IPA), ethanol, methanol, 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, a combination of DMSO and methanol, and a combination of DMSO and butanol. 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, and can be carried out, for example, by an ultrasonic homogenizer, a high-speed rotary homogenizer, other pulverization devices using cavitation phenomena, or obliquely impacting liquids with each other at a high pressure. The pulverizing device and the like. 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 medium-free method, and thus is subjected to high-speed shearing. The force is peeled off from the joint surface of the weakly bonded cerium oxide particles which have been contained in the three-dimensional structure of the gel. In this way, a new sol three-dimensional structure can be obtained by pulverizing the aforementioned gel-like bismuth compound. The aforementioned three-dimensional structure can maintain a void structure having a range of particle size distribution during the formation of the coating film, and the void structure can be formed again by stacking during 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 carry out pulverization so as to be a pulverized material having a particle size deviation (for example, a volume average particle diameter or a particle size distribution) as described above. It is assumed that when the amount of work such as the pulverization time and the strength is insufficient, not only the coarse particles may remain but the dense pores may not be formed, and the appearance defects may be increased, so that high quality cannot be obtained. On the other hand, when the amount of work is too large, for example, sol particles which are finer than the desired particle size distribution may be formed, and the size of the voids which are deposited after the coating is dried may be fine, and the desired void ratio may not be satisfied.

After the pulverization step, the ratio of the residual stanol groups contained in the pulverized material is not particularly limited, and may be, for example, the same as the range exemplified as the gelatinous ruthenium compound after the aging treatment.

After the pulverization step, the proportion of the pulverized material containing the solvent of the pulverized material is not particularly limited, and for example, the conditions of the coating material of the present invention mentioned in the foregoing can be exemplified. The ratio may be, for example, a condition in which the solvent itself of the ground product is contained after the pulverization step, or may be a condition adjusted before use as the paint after the pulverization step.

The coating material of the present invention can be produced by using the first coating material or the second coating material as described above. The first coating material contains a gelatinous ruthenium compound as described above, and the gelatinous ruthenium compound is obtained from a ruthenium compound containing at least a trifunctional or less saturated bond functional group. The method for producing the first coating material includes, for example, a gelation step in which the ruthenium compound is Gelation of the solvent to form a gelatinous quinone compound, for example, the description of the gelatinous quinone compound after the gelation step mentioned in the introduction. The second coating material contains a gelatinous ruthenium compound as described above, and the gelatinous ruthenium compound is a gelatinous substance obtained from a ruthenium compound containing at least a trifunctional or less saturated bond functional group, and has been subjected to a ripening treatment. The method for producing the second coating material includes, for example, a ripening step of aging the gelatinous quinone compound obtained from the hydrazine compound in a solvent, for example, the gelatinous hydrazine after the aging step mentioned in the introduction. Description of the compound.

The coating material of the present invention can be produced as described above, and contains a pulverized product of a gelatinous quinone compound and a dispersion medium. Further, a catalyst which can chemically bond the pulverized materials to each other in the above-described respective production steps or thereafter can be added to the coating material of the present invention. 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 pulverized product of the gelatinous quinone compound. The pulverized materials can be chemically bonded to each other by the catalyst, for example, in the bonding step described later. The catalyst may be, for example, a catalyst for promoting crosslinking and bonding of the pulverized materials to each other. The chemical reaction for chemically bonding the pulverized materials to each other preferably utilizes a dehydration condensation reaction of residual stanol groups 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 pulverized materials can be chemically bonded to each other (for example, cross-linked bonding) by the aforementioned photoactive catalyst, for example, without heating. Thereby, it is not easy to cause shrinkage by heating, so that a high void ratio can be maintained. In addition to the above-mentioned catalyst, a substance capable of generating a catalyst (catalyst can also be used) Producer) 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 thermoactive catalyst ( Heat catalyst generator) or replace it. The photocatalyst generating agent is not particularly limited, and examples thereof include a photobase generator (a catalyst that generates an alkaline catalyst by light irradiation), a photoacid generator (a substance that generates an acid catalyst by light irradiation), and the like. It is preferred to use a photobase agent. 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 pulverized materials to each other is not limited to the photoactive catalyst and the photocatalyst generating agent, and may be, for example, a thermal active catalyst or a thermal catalyst generating agent such as urea. The catalyst for chemically bonding the pulverized materials to each other 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. Among them, alkaline catalysts are preferred. The catalyst for chemically bonding the pulverized materials to each other, for example, may be added to a sol particle liquid (for example, a suspension) containing the pulverized material before being coated, or may be prepared by mixing the aforementioned catalyst to A mixture of solvents is used. 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, for example, a crosslinking auxiliary agent for indirectly bonding the pulverized materials of the gelled cerium compound to each other may be added to the coating material of the present invention. The crosslinking auxiliary agent can be combined with each other by the particles (the pulverized material), and the particles are separated from each other by the interaction or combination of the particles and the crosslinking auxiliary agent, thereby effectively combining the particles. Increase the strength. The crosslinking assistant is preferably a multi-crosslinked decane monomer. The multi-crosslinked decane monomer specifically has, for example, two or more and three or less alkoxy fluorenyl groups, and the chain length between the alkoxy fluorenyl groups may be 1 or more and 10 or less, and may contain elements 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(triethoxy) Mercapto, butane, bis(trimethoxyindenyl)butane, bis(triethoxyindenyl)pentane, bis(trimethoxyindenyl)pentane, bis(triethoxyindenyl)hexane, bis ( Trimethoxyindol), bis(trimethoxyindolyl)-N-butyl-N-propyl-ethane-1,2-diamine, cis-(3-trimethoxydecylpropyl) trimer Isocyanate, cis-(3-triethoxymercaptopropyl) trimer 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 pulverized material of the cerium compound.

[2. How to use the paint]

As a method of using the coating material of the present invention, a method for producing a porous polysiloxane porous body is exemplified below, but the present invention is not limited thereto. Further, the porous polysiloxane porous body produced by using the coating material of the present invention may be referred to as "the porous polysiloxane porous body of the present invention" hereinafter.

The method for producing a polysiloxane porous body characterized by, for example, comprising: a precursor forming step of forming the precursor of the polyfluorinated porous body using the coating material of the present invention; and a bonding step of causing the precursor The aforementioned pulverized materials containing the aforementioned coatings are chemically bonded to each other. The precursor may also be, for example, a coating film.

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

Since the coating material of the present invention used in the method for producing a porous polysiloxane porous body contains the pulverized material of the gelatinous cerium compound, the three-dimensional structure of the gelled cerium compound exhibits a state of being dispersed into a three-dimensional basic structure. Therefore, in the method for producing a porous polysiloxane porous body, When the foregoing precursor (for example, a coating film) is formed using the aforementioned coating material, the aforementioned three-dimensional basic structure is deposited to form a void structure mainly composed of the aforementioned three-dimensional basic structure. That is, according to the method for producing a porous polysiloxane, a novel three-dimensional structure which is distinct from the three-dimensional structure of the gel-like cerium compound and which is formed by the pulverized material of the three-dimensional basic structure described above can be formed. Further, in the method for producing a porous polysiloxane body, 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 method for producing a porous polysiloxane porous body has a structure having a void, and can maintain sufficient strength and flexibility. The polysiloxane porous body obtained by the present invention can be used, for example, as a member using voids in a wide range of products, such as a heat insulating material, a sound absorbing material, an optical member, an ink image receiving layer, etc., and can be made to have various functions. Laminated film.

The method for producing the porous polysiloxane porous body can be described along with the coating material of the present invention described above unless otherwise specified.

In the step of forming the precursor of the foregoing porous body, for example, the aforementioned coating of the present invention is applied onto the aforementioned substrate. The coating material of the present invention can be formed into a substrate, for example, after the coating film is dried, and the pulverized materials are chemically bonded to each other (for example, cross-linked) by a bonding step, and the film is continuously formed to have a certain degree or more. A void layer of film strength.

The coating amount of the coating material 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 polysiloxane porous body. In a specific example, when the porous polysiloxane porous body having a thickness of 0.1 to 1000 μm is formed, the coating amount of the coating material with respect to the substrate is 1 m ² in the area of the substrate, for example, the pulverized material is 0.01 to 60000 μg. , 0.1~5000μg, 1~50μg. The desired coating amount of the aforementioned coating material is, for example, related to the liquid concentration or the coating method, and the like, and thus it is difficult to make a single definition. If 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, before the nano-pulverized sol particles are deposited and accumulated in a solvent to form a void structure, the formation of voids may be inhibited by drying of the solvent, and the void ratio may be greatly lowered. On the other hand, when the coating amount is too thin, the risk of coating cissing due to the unevenness of the substrate, the hydrophobicity of the substrate, and the like may increase.

After the coating material is applied onto the substrate, the porous body precursor (coating film) may be subjected to a drying treatment. By the above-described drying treatment, it is intended to remove not only the solvent (the solvent contained in the coating material) in the precursor of the porous body but also the sol particles in the drying process to form a void structure. The temperature of the drying treatment is, for example, 50 to 250 ° C, 60 to 150 ° C, and 70 to 130 ° C, and the drying treatment time is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, or 0.3 to 3 minutes. With regard to the drying treatment temperature and time, for example, in the case of continuous productivity or the appearance of high void ratio, 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.

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. Further, for example, a small amount of a perfluoro-based surfactant or a quinone-based surfactant may be added to the above IPA or the like to reduce the surface tension.

The substrate is not particularly limited, and for example, a base material made of a thermoplastic resin, a base material made of glass, an inorganic substrate typified by ruthenium, a plastic or a semiconductor molded by a thermosetting resin, or the like, and a carbon nanotube are preferably used. The carbon fiber-based materials and the like are not limited by these. 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. Ethylene glycol (PEN), polyethylene (PE), polypropylene (PP), and the like.

In the method for producing a porous polysiloxane body, the bonding step is a step of chemically bonding the pulverized materials contained in the precursor (coating film) of the porous body to each other. By the aforementioned bonding step, for example, the three-dimensional structure of the pulverized material in the precursor of the porous body can be fixed. When it is fixed by conventional sintering, for example, it is made to be higher than 200 ° C. Warm treatment to stimulate the dehydration condensation of the stanol groups to form a decane linkage. 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 can be neither damaged or dried at a temperature of about 100 ° C. The void structure is continuously formed and fixed at a temperature and for a short processing time of only a few minutes.

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, for example, by chemical crosslinking of the pulverized materials. For example, when inorganic particles such as titanium oxide are added to the pulverized material, for example, the inorganic particles may be considered. It is chemically crosslinked with the aforementioned pulverized material. Further, in the case of providing a biocatalyst such as an enzyme, it is also possible to chemically crosslink other sites different from the active site of the catalyst with the pulverized material. Therefore, the present invention can be applied not only to the void layer (polyaluminum 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 the like. 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 kind of the pulverized material of the gelled cerium compound. The chemical reaction of the present invention is preferably carried out by a dehydration condensation reaction of a residual stanol group contained in the pulverized material of the gelled ruthenium compound. By the above-mentioned catalyst, the reaction between the hydroxyl groups of the stanol groups can be promoted, and the continuous film formation in which the void structure is hardened in a short time can be achieved. The catalyst may, for example, be an alkaline catalyst such as potassium hydroxide, sodium hydroxide or ammonium hydroxide, or an acid catalyst such as hydrochloric acid, acetic acid or oxalic acid, but is not limited thereto. The catalyst for the dehydration condensation reaction described above is preferably a basic catalyst. In addition, it is also suitable to use light that exhibits catalytic activity by irradiation with light (for example, ultraviolet rays). An acid generating catalyst, a photobase generating catalyst, a photoacid generator, a photobase generator, and the like. 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, and examples thereof include water, a buffer solution and the like.

The chemical reaction in the presence of the above-mentioned catalyst can be carried out, for example, by irradiating or heating the aforementioned coating film containing the above-mentioned catalyst and the aforementioned catalyst has been previously added to the aforementioned coating material; The film is sprayed with the above-mentioned catalyst, and then irradiated or heated by light; or light irradiation or heating is performed while spraying the above-mentioned catalyst. For example, when the catalyst is a photoactive catalyst, the pulverized materials may be chemically bonded to each other by light irradiation to form the porous polysiloxane porous body. Further, when the catalyst is a thermally active catalyst, the pulverized materials may be chemically bonded to each other by heating to form the porous polysiloxane porous body. The amount of light irradiation (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 it is preferable to use a cumulative amount of light of 200 mJ/cm ² or more. Further, in order to prevent the substrate under the void layer from being damaged and causing thermal wrinkles, it is preferable to use a cumulative amount of light of 800 mJ/cm ² or less. 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 is not limited thereto.

The polythene oxide porous body 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 polyaluminum oxide porous body of the present invention may be subjected to a step of heating and aging, for example, to increase the strength (hereinafter sometimes referred to as "aging step"). For example, when the polysiloxane porous body of the present invention is laminated on the resin film, the adhesion peeling strength with respect to the resin film can be improved by the strength increasing step (aging step). In the aforementioned strength increasing step (aging step), for example, the porous polysiloxane porous body of the present invention may 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 above-mentioned aging step, for example, by setting the heating temperature to a low temperature, the shrinkage of the porous polysiloxane porous body can be suppressed and the adhesive peel strength can be improved at the same time, thereby achieving both high void ratio and strength.

The phenomenon and mechanism of germination in the aforementioned strength-increasing step (aging step) are not known, and it is considered that the above-mentioned pulverized materials are chemically bonded to each other (for example, cross-linking), for example, by the catalyst contained in the porous polysiloxane porous body of the present invention. The reaction) is further developed to increase the strength. In a specific example, when the residual stanol group (OH group) is present in the porous polysiloxane body, the residual decane is The alcohol groups are chemically bonded to each other by a crosslinking reaction. Further, the catalyst contained in the porous polysiloxane porous body of the present invention is not particularly limited, and for example, it may be a catalyst used in the above-mentioned bonding step, and may be a photobase generating catalyst used in the above-mentioned bonding step by light. The alkaline substance generated by the irradiation may be an acidic substance generated by photo-irradiation of the photoacid generating catalyst used in the above-mentioned bonding step, or the like. However, this description is only an example and does not limit the invention.

Further, an adhesive layer (adhesive layer forming step) may be further formed on the porous polysiloxane porous body 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. At this time, the base material of the adhesive tape or the like may be maintained in a state of being bonded thereto, and 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, the "adhesive" and the "adhesive" are not clearly distinguishable, and the "adhesive layer" and the "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, examples of the water-soluble crosslinking agent such as glutaraldehyde, melamine, and oxalic acid may be used. Ingredients, etc. 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 porous polysiloxane porous body of the present invention may be reacted with the adhesive layer to form an intermediate layer disposed between the polysiloxane porous body of the present invention and the adhesive layer (intermediate layer forming step). By the intermediate layer, for example, the porous polysiloxane body 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, it may be the catalyst used in the foregoing bonding step, or may be the alkaline substance generated by the photobase polymerization catalyst used in the above-mentioned bonding step by light irradiation, or may be in the aforementioned bonding step. The photoacid used generates an acidic substance or the like which is generated by irradiation of light by a catalyst. Further, the reaction of the porous polysiloxane porous body of the present invention with the above-mentioned adhesive layer may be, for example, a reaction (for 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. Moreover, the intermediate layer forming step can also serve to enhance The aforementioned strength increasing step (aging step) of the strength of the polysiloxane porous body of the present invention.

The polyasperylene porous body 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, for example, each constituent element may be laminated by 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, and the base material can be a molded article or a component. Those who have been processed in batches are stacked.

Hereinafter, a method of forming the above-mentioned polyfluorinated porous body on a substrate by using the coating of the present invention described above will be exemplified in Figs. 2 shows a step of laminating a protective film and winding it after the production of the porous polysiloxane porous body, and the above method may be employed when laminating another functional film, or another function may be applied. After drying the film, the above-mentioned film-forming porous polysiloxane body is bonded before the film is being wound up. In addition, the film formation method shown in the figure is only an example, and is not limited to 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 the aforementioned coating material 20" of the present invention onto a substrate 10; and a coating film forming step (drying step) (2) The coating 20" is dried to form a coating film 20' which is the precursor layer of the polyfluorinated porous body; and a chemical treatment step (for example, a crosslinking treatment step) (3), which is a pair The coating film 20' is chemically treated (for example, crosslinked) to form Polysiloxane porous body 20. In this manner, the polysiloxane porous body 20 can be formed on the substrate 10 as illustrated. 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 coating material 20" is not particularly limited, and a general coating method may be employed. The coating method may be, for example, a slot die method or a reverse 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., etc., based on productivity, smoothness of coating film, etc. The extrusion coating method, the curtain coating method, the roll coating method, the micro gravure coating method, etc. are preferable. The coating amount of the coating material 20" is not particularly limited, and for example, a porous structure (polyfluorene) can be used. The oxygen porous body 20 is suitably set so as to have a suitable thickness. The thickness of the porous structure (polysiloxane porous body) 20 is not particularly limited and may be as described above.

In the aforementioned drying step (2), the coating material 20" is dried (i.e., the dispersion medium contained in the coating material 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 substrate 10 is unscrewed from the feeding roller 101, and after the coating roller 102 is subjected to the coating step (1), it is then moved to the drying step (2) in the oven region 110, the aforementioned coating step ( 1) coating the coating material 20" of the present invention on the substrate 10. In the coating apparatus of Fig. 2, the coating step (1) is followed by a pre-drying step before the drying step (2). The pre-drying step may not The heating is performed at room temperature. In the drying step (2), the heating mechanism 111 is used. As the foregoing, the heating mechanism 111 can suitably use a hot air heater, a heating roller, a far-infrared heater, etc. Further, for example, drying can be employed. Step (2) is divided into a plurality of steps to make the drying temperature higher and higher with the subsequent drying step.

After the drying step (2), the chemical treatment step (3) is carried out in the chemical treatment zone 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. Then, after the chemical treatment step (3), the substrate 10 is wound up by the take-up roll 105. A laminate of the polysiloxane porous body 20. Further, in Fig. 2, the porous structure 20 of the laminated body is covered and protected by a protective sheet which is unwound by the roller member 106. Here, another layer formed of a long film may be laminated on the porous structure 20 instead of the protective sheet.

Fig. 3 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 to 30 m/min.

First, the substrate 10 is unscrewed from the delivery roller 201, and a coating step (1) is applied to coat the substrate 20 on the substrate 10. The coating of the coating 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 coating material 20" retained in the liquid storage area 202 is attached to the surface of the micro-gravure plate 204, and then adjusted to a predetermined thickness by the doctor blade 203 while being applied to the surface of the substrate 10 by the micro-gravure plate 204. In addition, the micro gravure 204 For the sake of example, it is not limited thereto, and any other coating mechanism may be used.

Next, the drying step (2) is carried out. Specifically, the substrate 10 of the coated coating 20" is conveyed in the oven zone 210 and heated and dried by the heating mechanism 211 in the oven zone 210. The heating mechanism 211 can also be the same as that of Fig. 2, for example. For example, the drying step (2) can also be divided into a plurality of steps by dividing the oven zone 210 into a plurality of blocks, and the drying temperature is followed by the subsequent drying. The drying step is getting higher and higher. After the drying step (2), the chemical treatment step (3) is carried out in the chemical treatment zone 220. In the chemical treatment step (3), for example, when the coated film 20' after drying contains a photoactive catalyst, light is irradiated with a lamp (light irradiation means) 221 disposed above and below the substrate 10. Alternatively, for example, when the dried coating film 20' contains a thermally active catalyst, a hot air heater (heating mechanism) is used instead of the lamp (light irradiation device) 221 to arrange the air heater below the substrate 10 (heating mechanism) The substrate 10 is heated 221 . By the crosslinking treatment, the chemical combination of the above-mentioned 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 laminate of the porous polysiloxane porous body 20 is wound up on the substrate 10 by the take-up roll 251. 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. 4, the method is performed after the chemical treatment step (e.g., 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. 4, 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. 5 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 subjected to a chemical treatment step (3) The chemical treatment zone 120 is followed by a strength enhancement zone (maturing zone) 130 for performing a strength enhancement step (aging step) (4), which is otherwise identical to the device of FIG. That is, after the chemical treatment step (3), a strength-increasing step (aging step) (4) is performed in the strength-enhancing region (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, a laminated film in which the porous polysiloxane porous body 21 is formed on the substrate 10 is taken up by the take-up roll 105 in the same manner as in FIG.

Fig. 6 is a schematic view showing another example of a 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, in the same manner as in Fig. 3, a porous polysiloxane is formed on the substrate 10 by winding up the winding roller 251. The laminated film of the body 21.

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. 7, the method comprises: after the chemical treatment step (for example, the crosslinking treatment step) (3) of forming the polysiloxane porous body 20, coating the adhesive layer 30 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 7-9 are the same as those shown in Figures 4-6. Further, in Fig. 7, the intermediate layer forming step (5) also serves as a step of increasing the strength of the polysiloxane porous body 20 (strength enhancing step), and after the intermediate layer forming step (5), the polysiloxane porous body 20 is promoted. It is 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. 8 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 performing the adhesive layer coating step (4), and FIG. 5 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. 5 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, the apparatus of Fig. 8 is subjected to the adhesive layer coating after the chemical treatment step (3). a coating step (adhesive layer forming step) (4), that is, coating (coating) the adhesive on the polysiloxane porous body 20 by the adhesive layer coating mechanism 131a in the adhesive layer coating region 130a or The adhesive is then applied to form the 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 air heater (heating means) 131 are not particularly limited as described in the introduction.

Fig. 9 is a schematic view showing still another example of a coating apparatus of a micro gravure method (microgravure coating method) and a method of forming the 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. 6 The device is the same. In the same figure, the intermediate layer forming region (maturing region) 230 disposed immediately behind the adhesive layer coating region 230a can be made to have the strength with FIG. 6 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. 9, after the chemical treatment step (3), an adhesive layer coating step (adhesive layer formation step) (4) is performed, that is, by adhering the layer in the adhesive 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. Come again, An intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming region (curing zone) 230 to cause the polysiloxane porous body 20 to react 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. Polysiloxane porous body]

The polysiloxane porous body of the present invention is characterized in that the scratch resistance of the display film strength as described later by Bemcot (registered trademark) is 60 to 100%, and the flexural resistance obtained by the MIT test is 100 times. Above, but not limited to this.

In the polyaluminoxy porous system of the present invention, the pulverized material of the gelled ruthenium compound is used, and therefore the three-dimensional structure of the gelled ruthenium compound is broken to form a completely new three-dimensional structure which is distinct from the gelatinous ruthenium compound. In this way, the porous polysiloxane body of the present invention can form a high void ratio and be a layer by forming a layer of a new pore structure (new void structure) which is formed by a layer which cannot be formed of the gelatinous ruthenium compound. A meter-scale polysiloxane porous body. Further, the polyfluorene-containing porous system of the present invention chemically bonds the pulverized materials to each other while adjusting the number of the decane-bonding functional groups of the gel-like fluorene compound. Further, after the precursor is formed as a novel three-dimensional structure as the porous polysiloxane porous body, chemical bonding (for example, crosslinking) is carried out in the bonding step. Therefore, the porous polysiloxane porous body of the present invention has a structure of voids and can be maintained sufficiently. Strength and flexibility. Therefore, according to the present invention, the porous polysiloxane porous body can be easily and easily supplied to various objects. Specifically, this The polysiloxane porous body of the invention can be used, for example, as a heat insulating material, a sound absorbing material, a stent for regenerative medical treatment, a dew condensation preventing material, an optical member, or the like, instead of the air layer.

The polysiloxane porous body of the present invention is, for example, the same as the above-mentioned pulverized product generally containing a gelatinous cerium compound, and the pulverized materials are chemically bonded to each other. In the porous polysiloxane body of the present invention, the form of the chemical bond (chemical bond) between the pulverized materials is not particularly limited, and specific examples of the chemical bond include a cross-linking bond and the like. Further, the method of chemically bonding the above-mentioned pulverized materials to each other is as described in detail in the above-mentioned manufacturing method of the porous polysiloxane porous body.

The aforementioned crosslinking bond is, for example, a decane bond. The oxime bond can be exemplified by the T2 key, the T3 key, and the T4 key shown below. When the polysiloxane porous body of the present invention has a decane bond, for example, it may have any one of the bonds, and may have any two of them, or may have all three of them. 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, although the ratio of T4 in the above-mentioned decane bond is large, the film strength is likely to be exhibited, but the void size is small and the flexibility is 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-described decane bond, the ratio of T2, T3 and T4 is, for example, when T2 is represented by "1", and T2: T3: T4 = 1: [1 - 100]: [0~ 50], 1:[1~80]: [1~40], 1:[5~60]:[1~30].

Further, the porous polysiloxane porous body of the present invention is preferably a state in which, for example, the ruthenium atom contained is a ruthenium oxide bonded state. 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 polysiloxane porous body of the present invention has a pore structure, and the pore size of the pores means the long axis diameter of the void (hole) and the aforementioned major axis diameter in the minor axis diameter. The ideal pore size is, for example, 5 nm to 200 nm. 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, 1000 μm or less, 500 μm or less, or 100 μm or less, and the range thereof is, for example, 5 nm to 1000 μm, 10 nm to 500 μm, or 20 nm to 100 μm. The 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, the void size can be evaluated, for example, by the following method.

(evaluation of void size)

In the present invention, the aforementioned void size can be quantified by the BET test method. Specifically, after 0.1 g of a capillary input sample (polyporous porous oxygen body of the present invention) of a specific surface area measuring device (manufactured by Micromeritics Co., trade name: ASAP2020), the mixture was dried under reduced pressure at room temperature for 24 hours to form a void. The gas in the structure is degassed. 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 polysiloxane porous body of the present invention exhibits, for example, a film strength of Bemcot (registered trademark) using a scratch resistance of 60 to 100%. The present invention is excellent in scratch resistance in various processes because it has such a film strength. The present invention has scratch resistance in a production process in the case of winding and handling a film of a product after the production of the porous polysiloxane porous body, for example. On the other hand, in the polyaluminum oxide porous body of the present invention, for example, the catalyst reaction in the heating step described later can be used as an alternative to reducing the void ratio, and the particle size of the pulverized product of the gelled ruthenium compound and the pulverized material can be increased from each other. The binding force of the neck of the mutual oxime bond. 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 porous polysiloxane porous body 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) for the sample to measure the Si coating amount (Si ₀ ). Next, the void layer on the acrylic film was cut into 50 mm × 100 mm from the periphery 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 to detect the Si residual amount (Si ₁ ) after the scratch test. The scratch resistance is defined by the Si residual ratio (%) before and after the Bemcot (registered trademark) test, and can be expressed by the following formula.

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

The polyfluorene-containing porous body of the present invention exhibits, for example, flexibility, and the number of folding resistances obtained by the MIT test is 100 or more. Since the present invention has such flexibility, it is excellent in handleability such as winding or use during the production process.

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

(evaluation of the folding test)

The void layer (the porous polysiloxane porous body of the present invention) was cut into a short strip of 20 mm × 80 mm, and then mounted on a MIT folding tester (BE-202 manufactured by TESTER SANGYO CO., LTD.). 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 porous polysiloxane body 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 .

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

(Evaluation of membrane density)

After the void layer (the porous polysiloxane porous body of the present invention) was formed on the acrylic film, the X-ray reflectance of the total reflection region was measured using an X-ray diffraction apparatus (manufactured by RIGAKU Co., Ltd.: RINT-2000). After the Intensity and 2θ were prepared, the porosity (P%) was calculated from the critical angle of total reflection of the void layer ‧ substrate. The film density can be expressed by the following formula.

Film density (%) = 100 (%) - porosity (P%)

The porous polysiloxane body 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 porous polysiloxane porous body, 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 void ratio in the bulk can be increased, and when the closed foamed particles such as hollow cerium oxide are used, open foaming cannot be formed. structure. On the other hand, in the porous polysiloxane body of the present invention, since the cerium oxide sol particles (the pulverized product of the gel-like cerium compound forming the sol) have a three-dimensional tree structure, the coating film (containing the aforementioned gelatinous ruthenium) In the sol coating film of the pulverized product of the compound, the open foam structure can be easily formed by sedimentation and deposition of the dendritic particles. In addition, the present invention The polysiloxane porous body preferably forms an open foam structure having a plurality of pore distributions of a monolith structure. The monolithic structure refers to, for example, a structure in which fine voids having a nanometer size are present, and a hierarchical structure in which an open foamed structure in which the same nanovoids are aggregated exists. When the monolithic structure is formed, for example, the fine voids can be used to impart strength, and at the same time, the coarse open voids can be provided with a high void ratio, and the film strength and the high void ratio can be achieved. In order to form a monolithic structure such as the monolithic structure, for example, it is important to control the pore distribution of the void structure to be formed by the gelatinous ruthenium compound in the previous stage of pulverization into the pulverized material. Further, for example, when the gel-like cerium compound is pulverized, the particle size distribution of the pulverized material can be controlled to a desired size to form the monolithic structure.

In the porous polysiloxane body of the present invention, the elongation at which the tear is formed is not particularly limited, and the lower limit thereof is, for example, 0.1% or more, 0.5% or more, or 1% or more, and the upper limit thereof is, for example, 3% or less. The range of the tear formation elongation is, for example, 0.1 to 3%, 0.5 to 3%, or 1 to 3%.

The aforementioned tear generation elongation can be measured, for example, by the following method.

(Evaluation of elongation of tear marks)

After forming a void layer (the porous polysiloxane porous body of the present invention) on the acrylic film, a short strip sample of 5 mm × 140 mm was taken out. Then, the sample was placed in a tensile tester (AG-Xplus, manufactured by Shimadzu Corporation) with a distance between the clamps of 100 mm, and then subjected to a tensile test at a tensile speed of 0.1 mm/s. Carefully observe the aforementioned sample in the test and end the test at the time when a part of the aforementioned sample is cracked, and at the time point when the crack occurs The elongation (%) is the elongation at which the tear marks are generated.

In the porous polysiloxane body 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, 10% or less, 5% or less, or 3 Below %, the range is, for example, 0.1 to 10%, 0.2 to 5%, and 0.3 to 3%.

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

(haze evaluation)

The void layer (the porous polysiloxane porous body 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 porous polysiloxane porous body of the present invention is not particularly limited, and the upper limit thereof is, for example, 1.3 or less, less than 1.3, 1.25 or less, 1.2 or less, and 1.15 or less, and the lower limit thereof is, for example, 1.05 or more, 1.06 or more, or 1.07 or more. For example, it is 1.05 or more and 1.3 or less, 1.05 or more, less than 1.3, 1.05 or more, 1.25 or less, 1.06 or more, less than 1.2, and 1.07 or more and 1.15.

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.

(refractive index evaluation)

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

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

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

The method for producing the porous polysiloxane porous body of the present invention is not particularly limited, and it can be produced, for example, by the method for producing a porous porous oxygen body as mentioned in the above.

[4. Use of polyfluorene porous body]

The porous polysiloxane porous body produced by using the coating material of the present invention can exhibit the same function as the air layer as described above, and therefore can be used in the object having the air layer instead of the air layer.

The member containing the porous polysiloxane porous body may, for example, be a heat insulating material, a sound absorbing material, a dew condensation preventing material, or an optical member. These members can be arranged, for example, for use in a portion where an air layer is required. The form of the members is not particularly limited and may be, for example, a film.

Further, the member containing the porous polysiloxane porous body may be a stent for regenerative medical treatment. As mentioned in the introduction, the aforementioned polyaluminum oxide porous body can be exerted A porous structure that functions as an air layer. The pores of the porous polysiloxane porous body are suitable for holding, for example, cells, nutrient sources, air, and the like, and thus the porous structure can be effectively used as, for example, a stent for regenerative medicine.

The member containing the porous polysiloxane porous body may be, in addition to these, a total reflection member, an ink image receiving material, a single layer AR (anti-reflection), a single layer moth eye, and a dielectric constant material. 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 coating material and the porous structure (polyfluorinated porous body) of the present invention were produced in the following manner.

(1) Gelation of bismuth compounds

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

After adding 0.88 g of 28% ammonia water and 0.2 g of pure water to 5.5 g of DMSO, the above-mentioned hydrolyzed mixture was added thereto, and stirred at room temperature for 15 minutes to prepare a ginseng (hydroxy)methyl decane gel. A gelatinous quinone compound was obtained.

(2) ripening treatment

The gelled mixture was directly cultured 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 becomes a sol liquid of the pulverized product. The result of confirming the volume average particle diameter by a dynamic light scattering type Nanotrac particle size analyzer (manufactured by Nikkiso Co., Ltd., UPA-EX150 type) was 0.50 to 0.70, and the volume average particle diameter indicates the pulverized material contained in the mixed liquid. Particle size deviation. Further, a 0.3 wt% aqueous KOH solution was prepared, and 0.02 g of catalyst KOH was added to 0.5 g of the sol solution to prepare a coating liquid (catalyst-containing paint).

(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 has 6 μL of the sol liquid per 1 mm ^{2 of the} surface of the substrate. The coating film was treated at a temperature of 100 ° C for 1 minute to complete the film formation of the precursor of the polysiloxane porous body and the crosslinking reaction of the foregoing pulverized materials of the precursor. 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.

(Example 2)

An IPA (isopropyl alcohol) solution of 1.5% by weight of a photobase generating catalyst (Wako Pure Chemical Industries, Ltd.: trade name WPBG266) was prepared, and 0.731 g of the sol particle liquid was added to the KOH 0.031 g of Example 1 to prepare a solution. The coating liquid was subjected to the same operation as in Example 1 except that UV irradiation of 350 mJ/cm ² (@360 nm) was carried out after the formation of the coating film, and a porous polysiloxane porous body was obtained on the substrate. Further, the porous body was heated and aged at 60 ° C for 20 hr to further increase the film strength.

(Example 3)

In the coating liquid described in Example 2, 0.018 g of 5% by weight of bis(trimethoxyindenyl)ethane was added to 0.75 g of the sol solution, and the same operation as in Example 2 was carried out to obtain a polymerization. Helium oxygen porous body.

(Comparative Example 1)

A porous body was formed in the same manner as in Example 1 except that the culture in the ripening step was changed to 40 ° C for 72 hours.

(Comparative Example 2)

The same method as in Example 1 except that TEOS (tetramethoxysilane) was used as the precursor of the hydrazine compound, and the culturing step was carried out, and the culturing step was changed to 40 ° C for 72 hours. A porous body is formed. Further, in the comparative example, when the porous body (film) was made to have a thickness of 1 μm, the film was partially broken, so that the thickness was changed to 200 nm to form a film.

The refractive index, the ratio of the residual stanol group, and the scratch resistance were measured for Example 1, Comparative Example 1, and Comparative Example 2. These results are shown in Table 1 below.

As shown in the above Table 1, the polysiloxane porous body (void layer) formed using the sol solution obtained in Example 1 was confirmed to have a thickness of 1 μm and a refractive index of less than 1.2, and the film strength was also easily obtained. Further, although not shown in Table 1, in Examples 2 and 3, the low refractive index was also confirmed and the film strength was high. On the other hand, when the sol solution of Comparative Example 1 was used, since the aging was carried out for a long period of time, almost no stanol group remained in the gel. Therefore, a crosslinked structure is not formed in the bonding step, and sufficient film strength cannot be obtained. Further, in the sol solution of Comparative Example 2, TEOS was used as the precursor of the ruthenium compound, and therefore, although a high film strength was obtained, the flexibility was also remarkably lowered. Therefore, it has been found that it is extremely useful to adjust the ruthenium compound precursor and the residual stanol group in order to achieve both film strength and flexibility.

(Example 4)

In the present embodiment, the coating material and the porous structure (polyfluorinated porous body) of the present invention were 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. Next, a 0.3% by weight aqueous solution of KOH was replaced, and a solution of 1.5% by weight of a photobase generating catalyst (Wako Pure Chemical Industries, Ltd.: trade name WPBG266) in IPA (isopropyl alcohol) was added to the sol particle liquid. Other than the same as in the first embodiment In the above-described "(3) pulverization treatment", a coating liquid (catalyst-containing paint) was prepared. The amount of the IPA solution to which the photobase generating catalyst was added was 0.031 g based on 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 UV irradiation was light having a wavelength of 360 nm, and the amount of light irradiation (energy) was set to 500 mJ. Further, 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 5)

A coating material and a porous structure (polyfluorinated porous body) were formed in the same manner as in Example 4 except that the heating and aging were not carried out after the irradiation of UV.

(Example 6)

After adding the IPA solution of the photobase to the catalyst, the same operation as in Example 4 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. A coating material and a porous structure (polysilicon porous body) are formed.

(Example 7)

A coating material and a porous structure (polyfluorinated porous body) were formed in the same manner as in Example 4 except that the amount of the IPA solution of the photo-base generating catalyst was changed to 0.054 g.

(Example 8)

After irradiating the dried porous body with UV in the same manner as in Example 4, the adhesive side of the PET film coated with the adhesive (adhesive layer) on one side was attached to the foregoing at room temperature before the heating and aging. After the porous body, at 60 The mixture was aged by heating at ° C for 22 hr. Otherwise, the same operation as in Example 4 was carried out to form a coating material and a porous structure (polysiloxane porous body).

(Example 9)

A coating material and a porous structure (polyfluorinated porous body) were formed in the same manner as in Example 8 except that the PET film was not attached and then heated and aged.

(Embodiment 10)

After the IPA solution of the photobase generating catalyst was added, 0.018 g of 5% by weight of bis(trimethoxy)decane was further added to 0.75 g of the sol solution to adjust the coating liquid, and the same operation as in Example 8 was carried out. The coating and the porous structure (polysilicon porous body) are formed.

(Example 11)

A coating material and a porous structure (polyfluorinated porous body) were formed in the same manner as in Example 8 except that the amount of the IPA solution in which the photobase generating catalyst was added was 0.054 g.

With respect to the porous structures of Examples 4 to 11, the refractive index, the adhesive peel strength, and the haze were measured by the above methods, and the results are shown in Tables 2 and 3 below. However, in the measurement of the adhesive peel strength of Examples 6 to 9, the laminated film webs were bonded to the PET film and the adhesive layer, and the adhesion of the PET film and the acrylic adhesive was omitted. Further, the storage stability of the coating liquids (catalyst-containing coatings) of Examples 4 to 11 was also shown in Tables 2 and 3. The storage stability was obtained by visually confirming whether or not the coating liquid was changed after leaving the coating liquid at room temperature for one week.

As shown in the above Tables 2 and 3, in the polyaluminum oxide porous bodies of Examples 4 to 11 which were obtained to have a thickness of 1 μm, the refractive indices were all extremely low at 1.14 to 1.16. Further, these ultra-low refractive index layer haze values all showed an extremely low value of 0.4, and thus it was confirmed that the transparency was extremely high. Further, since the ultra-low refractive index layers of Examples 4 to 11 had high adhesive peeling strength, it was confirmed that even if the wound body was wound up, it still had high strength which was not easily peeled off from the other layers of the laminated film roll. Further, the porous polysiloxane bodies of Examples 4 to 11 were confirmed to have extremely high scratch resistance. Further, in the coating liquids (catalyst-containing coating materials) of Examples 4 to 11, it was confirmed that no change was observed by visual observation after one week of storage, and it was confirmed that the storage stability was good, and it was possible to efficiently produce a stable quality polyfluorene. Oxygen porous body.

Industrial availability

As described above, the paint obtained by the production method of the present invention contains the pulverized product of the gelatinous ruthenium compound and the pulverized material contains a residual stanol group, so that the coating film is formed, for example, by using the above-mentioned paint, and the above coat is applied. The above-mentioned pulverized material of the film is chemically bonded to produce a porous structure having voids. As a result, the aforementioned porous structure formed using the foregoing coating material can exhibit the same function as the air layer as mentioned in the foregoing. Further, as described above, since the porous structure can be fixed by chemically bonding the pulverized materials to each other, the porous structure obtained has a structure of voids, and sufficient strength can be maintained. Therefore, the porous structure can easily and easily impart a porous liquid of stanol to various objects. Specifically, the porous structure of the present invention can be used as a heat insulating material, a sound absorbing material, a stent for regenerative medical treatment, a dew condensation preventing material, an optical member, or the like, for example, instead of the air layer. Therefore, the production method of the present invention and the coating prepared therefrom can, for example, be effective in producing a porous structure as mentioned in the introduction.

Claims (17)

A polyphosphonium oxysol coating material comprising: a pulverized product of a gelatinous cerium compound and a dispersion medium, wherein the gelatinous cerium compound is obtained from a cerium compound containing at least a trifunctional or less saturated functional group; The pulverized material contains 1 mol% or more of residual stanol groups; and the polydecane sol coating is a coating for chemically bonding the pulverized materials to each other. The coating material of claim 1, wherein the pulverized material has a volume average particle diameter of 0.05 to 2.00 μm. The coating material according to claim 1 or 2, wherein the hydrazine compound is a compound represented by the following formula (2); in the formula (2), X is 2 or 3, and R ¹ and R ² are each a linear alkyl group or a branch; The alkyl group, R ¹ and R ² may be the same or different from each other, and R ¹ may be the same or different from each other when X is 2, and R ² may be the same or different from each other; The coating material of claim 1 or 2, which contains a catalyst for chemically bonding the pulverized materials to each other. The coating material of claim 1 or 2, further comprising a crosslinking auxiliary agent for indirectly bonding the pulverized materials to each other. The coating material of claim 5, wherein the content of the crosslinking auxiliary agent is 0.01 to 20% by weight based on the weight of the pulverized material. A coating material comprising a gelatinous cerium compound and a raw material for producing the polyfluorene oxysol coating according to any one of claims 1 to 6, the gelatinous cerium compound having at least three functional groups The following saturated bond functional group of ruthenium compounds are prepared. A coating material comprising a gelatinous cerium compound and a raw material for producing the polyfluorene oxysol coating according to any one of claims 1 to 6, the gelatinous cerium compound having at least three functional groups The gel of the following saturated bond functional group of ruthenium compound was prepared and subjected to ripening treatment. A method for producing a polyphosphonium oxysol coating material according to any one of claims 1 to 6, characterized by comprising a mixing step of mixing a pulverized material of a gelatinous quinone compound with a dispersion medium, the gelatinous mash The compound is prepared from a ruthenium compound containing at least a trifunctional or less saturated bond functional group. The method of claim 9, further comprising the step of adding a crosslinking auxiliary agent for indirectly bonding the pulverized materials of the gelatinous cerium compound to each other in the mixing step. The method of claim 10, wherein the crosslinking auxiliary agent is added in an amount of 0.01 to 20% by weight based on the weight of the pulverized product of the gelatinous quinone compound. The production method according to any one of claims 9 to 11, further comprising a pulverization step of pulverizing the gelatinous ruthenium compound in a solvent; and the pulverization obtained by the pulverization step in the mixing step. The method of claim 12, further comprising a gelation step of forming the gelatinous ruthenium compound by gelling the ruthenium compound in a solvent; and using the gelation step by the pulverization step The aforementioned gelatinous quinone compound obtained. The method of claim 13, further comprising a step of aging the gelatinous quinone compound in a solvent, and wherein the gelating step is the gelatinous quinone compound after the aging step. The production method according to claim 14, wherein the gelatinous quinone compound is cultured at a temperature of 30 ° C or higher in the solvent in the ripening step. A method for producing a coating material according to claim 7, which comprises a gelation step of gelling a cerium compound in a solvent to form a gelatinous cerium compound containing at least a trifunctional or less saturated bond Functional group. A method for producing a coating material according to claim 8, characterized by comprising a step of aging a gelatinous hydrazine compound in a solvent, the gelatinous quinone compound being composed of a saturated bond functional group containing at least 3 functional groups or less Made from ruthenium compounds.