TWI691559B - Paint and its manufacturing method - Google Patents

Abstract

The purpose of the present invention is to provide a gap with strength and flexibility Structural paint.

The coating of the present invention is characterized by the crushing of gel-like silicon compounds And the dispersing medium, and the pulverized product contains residual silanol groups, and the gel-like silicon compound is made of a silicon compound containing at least 3 functional groups or less saturated bond functional groups. The method for producing a coating material of the present invention is characterized by, for example, including a mixing step of gelling a silicon compound containing at least 3 functional saturated bond functional groups and mixing the gel-like silicon compound and a dispersion medium. With the coating material of the present invention, for example, a coating film can be formed by coating on a substrate, and the pulverized substances contained in the coating film can be chemically combined with each other to form a porous structure.

Description

Paint and its manufacturing method Field of invention

The invention relates to a paint and a manufacturing method thereof.

Background of the invention

There have been various discussions on the sol solution for the silanol porous body that can use a silicon compound material (silicon compound material) as a raw material to form a void structure. The common point of these is that after the silicone compound is gelled, a crushed sol solution obtained by crushing the gelled silicone compound is prepared and applied to form a void structure. However, in order to obtain a higher porosity, there is a problem that the film strength of the silanol porous body is significantly reduced, and it is difficult to easily produce the silanol porous body industrially. Examples of taking into account the high porosity and strength are examples of application to anti-lens reflective layers (for example, refer to Patent Documents 1 to 4). In this method, after forming a void layer on the lens, it is fired at a high temperature of 150°C or longer for a long time, but the gel using tetraethoxysilane (TEOS) as a raw material has poor flexibility, so it may not The problem of forming a porous body on a solid substrate. In addition, there are application examples of the void layer that has not been subjected to firing treatment (for example, refer to Non-Patent Document 1). However, in this method, the silanol pulverized sol contains a large amount of residual silanol groups and is not baked after the formation of the void layer. Therefore, the obtained porous body has poor membrane strength and cannot be provided. The subject of impact resistance.

In order to solve these problems, attempts are being made to develop a thin film that can replace the air layer formed by the gap between the members.

Prior technical literature Patent Literature

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

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

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

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

Non-patent literature

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

Summary of the invention

In the past, there has never been any research report on obtaining a sol coating that can easily take into account the void layer of film strength and flexibility. Therefore, an object of the present invention is to provide a silanol sol paint having a high porosity (void ratio), a film strength, and a flexible void layer that can be easily formed into a film by continuous processing, for example.

In order to achieve the foregoing object, the polysilicone sol coating of the present invention is characterized by containing a pulverized product and a dispersion medium of a gel-like silicon compound, and the gel-like silicon compound is composed of a functional group containing at least 3 or less saturated bonds Manufactured from silicon compounds; the aforementioned crushed material contains more than 1 mole% of residual silicon Alkanol group, and the polysilica sol coating is a coating used to chemically bond the pulverized materials to each other.

The manufacturing method of the polysilicone sol paint of the present invention is characterized by comprising a step of mixing the crushed material of the gel-like silicon compound and the dispersion medium, and the gel-like silicon compound is functionalized by containing at least 3 functional saturated bonds Based on silicon compounds.

The first coating raw material of the present invention is characterized in that it contains a gel-like silicon compound and is used as a raw material for producing the polysilicone sol coating of the present invention, and the gel-like silicon compound is saturated with at least 3 functions or less It is prepared by bonding functional silicon compound.

The first method for producing a coating material of the present invention is characterized by including a gelation step in which a silicon compound containing at least 3 or less saturated bond functional groups is gelated in a solvent to produce a gel-like silicon compound.

The second coating material of the present invention is characterized in that it contains a gel-like silicon compound and is used to produce the aforementioned polysilica sol coating of the present invention, and the gel-like silicon compound contains at least 3 functional or less saturated bonds A gel made of a silicon compound with functional groups and subjected to ripening treatment.

The second method for manufacturing a coating material of the present invention is characterized by including a maturation step in which a gel-like silicon compound is matured in a solvent, and the gel-like silicon compound is composed of silicon containing at least 3 or less saturated bond functional groups Compound prepared.

The polysilicone sol paint of the present invention contains the pulverized material of the gel-like silicon compound, which can chemically combine the pulverized materials. therefore, For example, in the coating film using the above-mentioned paint, the polysiloxane porous body having voids can be manufactured by chemically combining the pulverized materials with each other.

The inventors of the present invention have conducted a detailed study and found that for the gel-like silanol compound, by remaining the silanol group, the pulverized products can be chemically combined with each other. Furthermore, it has been found that the polysilica sol coating according to the present invention can form a polysiloxane porous body easily and simply by forming a coating film and chemically combining the pulverized materials in the coating film with each other, for example. A void layer that balances strength and flexibility. According to the polysilicone sol paint of the present invention, for example, the aforementioned silanol porous body can be applied to various objects. Specifically, the polysilicon porous body obtained by using the polysilicone sol paint of the present invention can be used as a heat insulating material, a sound absorbing material, a stent material for regenerative medicine, a dew condensation preventing material, an optical member, etc., instead of the air layer. Therefore, the polysilicone sol paint and its manufacturing method of the present invention can effectively manufacture, for example, the aforementioned polysilicone porous body.

10‧‧‧ Base material

20‧‧‧Porous structure

20’‧‧‧Coated film (precursor layer)

20”‧‧‧Paint

21‧‧‧Strengthened porous structure

101、201‧‧‧sending roller

102‧‧‧Coating roller

105, 251‧‧‧ Take-up roller

106‧‧‧Roller

110, 210‧‧‧ oven area

111,131,231‧‧‧Heater (heating mechanism)

120, 220‧‧‧ chemical treatment area

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

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

130, 230‧‧‧ Intermediate layer formation area

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

202‧‧‧Liquid storage area

203‧‧‧ doctor knife

204‧‧‧ Microgravure

211‧‧‧Heating mechanism

FIG. 1 is a step cross-sectional view schematically showing an example of a method for forming a polysilicon porous body 20 on a substrate 10 using the coating material of the present invention.

FIG. 2 is a diagram schematically showing an example of a part of the steps for manufacturing a polysilicon porous body using the coating material of the present invention and an example of the equipment used.

FIG. 3 is a diagram schematically showing a part of the steps for manufacturing the polysilicon porous body using the coating material of the present invention and another example of the apparatus used.

FIG. 4 is a one-step cross-sectional view schematically showing another example of a method of forming a polysilicon porous body on a substrate in the present invention.

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

FIG. 6 is a diagram schematically showing a part of the steps for manufacturing the polysilicon porous body using the coating material of the present invention and still another example of the apparatus used.

FIG. 7 is a one-step cross-sectional view schematically showing still another example of the method of forming a polysilicon porous body on a substrate in the present invention.

FIG. 8 is a diagram schematically showing a part of the steps for manufacturing a polysilicon porous body using the coating material of the present invention and still another example of the apparatus used.

FIG. 9 is a diagram schematically showing a part of the steps for manufacturing the polysilicon porous body using the coating material of the present invention and still another example of the apparatus used.

Forms for carrying out the invention

In the paint of the present invention, for example, the volume average particle diameter of the pulverized product is 0.05 to 2.00 μm. However, in the present invention, the shape of "particles" (for example, the particles of the pulverized product, etc.) is not particularly limited, and may be spherical or non-spherical, for example. In the present invention, the particles of the pulverized product may be, for example, sol-gel beaded particles, nanoparticles (hollow nanosilica·nanosphere particles), nanofibers, and the like.

In the paint of the present invention, for example, the aforementioned silicon compound is a compound represented by formula (2) described later.

The coating material of the present invention contains, for example, a catalyst for chemically bonding the aforementioned pulverized products.

The method for producing a paint of the present invention further includes, for example, a pulverizing step of pulverizing the gel-like silicon compound in a solvent, and using the pulverized product obtained by the pulverizing step in the mixing step.

The manufacturing method of the paint of the present invention further includes, for example, a gelation step of gelating the silicon compound in a solvent to generate a gel-like silicon compound, and using the gel obtained by the generation step in the pulverization step Silicon compound.

The manufacturing method of the paint of the present invention further includes, for example, a aging step of aging the gel-like silicon compound in a solvent, and using the gel-like silicon compound after the aging step in the gelation step.

In the method for producing a paint of the present invention, for example, in the aging step, the gel-like silicon compound is cultured in the solvent at a temperature of 30° C. or higher and cooked.

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

[1. Paint and its manufacturing method]

As mentioned above, the polysilicone sol coating of the present invention is characterized in that it contains a pulverized product of a gel-like silicon compound and a solvent and the gel-like silicon compound is prepared from a silicon compound containing at least 3 functional saturated bond functional groups or less The pulverized product contains residual silanol groups, and the polysilicone sol coating of the present invention is a coating for chemically combining the pulverized products with each other. "Saturated bond functional group containing less than 3 functional groups" means that the silicon compound has less than 3 functional groups and these functional groups form a saturated bond with silicon (Si).

As mentioned above, the method for manufacturing the coating of the present invention is the method for manufacturing the polysilicone sol coating of the present invention, which is characterized by comprising the steps of mixing the crushed material of the gel-like silicon compound and the dispersion medium. The compound consists of a silicon compound containing at least 3 functional saturated bond groups or less Material.

As described later, the coating material of the present invention can be used to produce a polysilicon porous body that can perform the same function as the air layer (for example, low refractive index). Specifically, the paint produced by the manufacturing method of the present invention contains a pulverized product of the gel-like silicon compound, and the pulverized product is the three-dimensional structure of the un-pulverized gel-like silicon compound that is damaged to form the unpulverized A completely new three-dimensional structure of gel-like silicon compounds. Therefore, for example, the coating film (precursor of polysilicon porous body) formed by using the aforementioned coating will become a new pore structure (new void structure) that cannot be formed by the layer formed by the aforementioned uncrushed gel-like silicon compound ) Layer. Thereby, the aforementioned layer can exert the same function as the air layer (for example, the same low refractive index). In addition, since the coating material of the present invention contains residual silanol groups, the coating film (precursor of polysilicon porous body) is used to form a completely new three-dimensional structure, so that the crushed materials can be chemically combined with each other. In this way, although the formed polysilicon porous body has a void structure, it can maintain sufficient strength and flexibility. Therefore, according to the present invention, the polysilicon porous body can be easily and simply supplied to various objects. The coating material produced by the manufacturing method of the present invention is very useful, for example, in the production of the aforementioned porous structure that can be used as a substitute for the air layer. In addition, in the case of the air layer, in the past, for example, it is necessary to provide a layer with a gap between the member and both members separated by a separator, etc., to form an air layer between the members. However, the polysiloxane porous body formed using the coating material of the present invention only needs to be disposed on the target site, and can perform the same function as the air layer. Therefore, as described above, it is easier and easier to give various objects the same function as the air layer than to form the air layer. Specifically, the aforementioned porous structure can be used as a heat insulating material, a sound absorbing material, a stent material for regenerative medicine, a dew condensation preventing material, etc., instead of the air layer, for example.

The coating material of the present invention may be, for example, a coating material for forming a porous silicone body or a coating material for forming a low-refractive layer. In the paint of the present invention, the aforementioned gel-like silicon compound is a pulverized product.

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

In addition, in the coating material of the present invention, the particle size distribution of the pulverized product is not particularly limited, for example, particles with a particle size of 0.4 μm to 1 μm are 50 to 99.9% by weight, 80 to 99.8% by weight, 90 to 99.7% by weight, or The particles with a particle size 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 product in the coating material of the present invention. The aforementioned particle size distribution can be measured by, for example, a particle size distribution evaluation device or an electron microscope.

In the paint of the present invention, the silicon 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, R ¹ and R ² are straight-chain alkyl or branched alkyl, R ¹ and R ² may be the same or different from each other, 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. In addition, for the aforementioned R ^2, for example, the example of R ^{1 in} formula (1) described later can be used.

Specific examples of the silicon compound represented by the aforementioned formula (2) include compounds represented by the following formula (2′) where X is 3. In the following formula (2'), R ¹ and R ² are the same as in the above formula (2). When R ¹ and R ² are methyl groups, the aforementioned silicon compound is trimethoxy (methyl) silane (hereinafter also referred to as “MTMS”).

In the coating of the present invention, the concentration of the crushed product of the gel-like silicon compound in the dispersion medium is not particularly limited, for example, it is 0.3-50% (v/v), 0.5-30% (v/v), 1.0~10%(v/v). Once the concentration of the aforementioned crushed material is too high, for example, the fluidity of the sol solution may be significantly reduced and Condensation and smearing occurred during coating. On the other hand, once the concentration of the pulverized product is too low, for example, not only does it take a considerable amount of time to dry the solvent, but also the residual solvent immediately after drying increases, so the porosity may decrease. In addition, in the coating of the present invention, for example, it is preferable that the silicon atoms contained are bonded with siloxane. As a specific example, the ratio of unbonded silicon atoms (that is, residual silanol) in the total silicon atoms contained in the aforementioned coating 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 aforementioned coating is, for example, at a shear rate of 10001/s, such as: viscosity below 100 cPa‧s, viscosity below 10 cPa‧s, and viscosity below 1 cPa‧s. Once the shear viscosity is too high, for example, coating marks may occur and the transfer rate of gravure coating may be reduced. Conversely, once the shear viscosity is too low, for example, the wet coating thickness during coating may not be increased and the desired thickness may not be obtained after drying.

In the coating material of the present invention, the dispersion medium (hereinafter also referred to as "coating solvent") is not particularly limited, and examples thereof include a gelation solvent and a grinding solvent described below, and the grinding solvent is preferably the aforementioned. Examples of the solvent for coating include organic solvents having a boiling point of 130° C. or lower. Specific examples include IPA, ethanol, methanol, and butanol.

The paint of the present invention may contain, for example, a catalyst for chemically bonding the crushed products of the gel-like silicon compound. The content of the catalyst is not particularly limited, and it is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight with respect to the weight of the pulverized product of the gel-like silicon compound.

In addition, the coating material of the present invention may further contain a cross-linking auxiliary agent for indirectly bonding the crushed products of the gel-like silicon compound, for example. The content of the cross-linking auxiliary agent is not particularly limited. For example, it is 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight with respect to the weight of the pulverized product of the gel-like silicon compound.

The coating material of the present invention is, for example, the sol-like pulverized product dispersed in the solvent, so it is also called, for example, "sol particle liquid". For example, the coating material of the present invention can be applied to a substrate and dried, and then chemically cross-linked through a bonding step to continuously form a void layer having a film strength of a certain degree or more. In addition, the "sol" in the present invention means that the three-dimensional structure of the gel is pulverized, so that the pulverized product (that is, the silica dioxide sol particles having the nano three-dimensional structure that retains a part of the void structure) is dispersed in the solvent and appears to flow Sexual status.

The manufacturing method of the present invention will be described below, and the coating of the present invention may be used as described below.

In the manufacturing method of the present invention, the mixing step is the step of mixing the pulverized product of the gel-like silicon compound and the dispersion medium as described above, and the gel-like silicon compound is composed of functional groups containing at least 3 or less saturated bonds Made of silicon compounds. In the present invention, the pulverized product of the gel-like silicon compound can be prepared from the gel-like silicon compound by, for example, a pulverization step described later. Therefore, the aforementioned gel-like silicon compound may also be referred to as the first coating material of the coating of the present invention, for example. In addition, the pulverized product of the gel-like silicon compound can be produced, for example, by the pulverization step described below from the gel-like silicon compound after the aging process of the aging step described later. Therefore, the aforementioned ripening The aforementioned gel-like silicon compound after the treatment can also be referred to as the second coating material of the coating of the present invention, for example.

In the production method of the present invention, the gelation step is a step of gelating the silicon compound containing at least 3 functional groups or less of a saturated bond functional group in a solvent to produce a gel-like silicon compound (first coating material). The aforementioned gelation step is, for example, a step of gelating the aforementioned silicon compound of the monomer by a dehydration condensation reaction in the presence of a dehydration condensation catalyst, whereby a gel-like silicon compound can be obtained. As described above, the gel-like silicon compound has residual silanol groups, and the residual silanol group is suitably adjusted in accordance with the chemical combination of the pulverized products of the gel-like silicon compound described later.

In the gelation step, the silicon compound is not particularly limited, as long as it is gelled by a dehydration condensation reaction. By the aforementioned dehydration condensation, for example, the aforementioned silicon compounds can be combined. The bonding between the aforementioned silicon compounds is, for example, hydrogen bonding or intermolecular force bonding.

The aforementioned silicon compound can be exemplified by the following formula (1). Since the silicon compound of the aforementioned formula (1) has a hydroxyl group, the silicon compounds of the aforementioned formula (1) can be hydrogen bonded or intermolecularly bonded through the respective hydroxyl groups, for example.

In the aforementioned 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 the aforementioned R ^{1 is} , for example, 1 to 6, 1 to 4, and 1 to 2. Examples of the linear alkyl group include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, and examples of the branched alkyl group include isopropyl group and isobutyl group. The aforementioned X is, for example, 3 or 4.

Specific examples of the silicon compound represented by the aforementioned formula (1) include compounds represented by the following formula (1′) where X is 3. In the following formula (1′), R ^{1 is the} same as the aforementioned formula (1), and is, for example, a methyl group. When R ¹ is a methyl group, the aforementioned silicon compound is ginseng (hydroxy) methyl silane. When X is 3, the silicon compound is, for example, trifunctional silane having three functional groups.

In addition, specific examples of the silicon compound represented by the above formula (1) include compounds in which X is 4. At this time, the aforementioned silicon compound is, for example, a tetrafunctional silane having four functional groups.

The silicon compound may be a precursor for forming the silicon compound of the formula (1) by hydrolysis, for example. As the precursor, for example, as long as it can generate the silicon compound by hydrolysis, specific examples include the compound represented by the formula (2).

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

The aforementioned hydrolysis method is not particularly limited, and for example, it can be carried out by a chemical reaction in the presence of a catalyst. Examples of the aforementioned catalyst include acids such as oxalic acid and acetic acid. For the aforementioned hydrolysis reaction, for example, an aqueous solution of oxalic acid can be After slowly dropping and mixing into the dimethyl sulfoxide solution of the aforementioned silicon compound precursor, stirring is carried out for about 30 minutes. When hydrolyzing the aforementioned silicon compound precursor, for example, the alkoxy group of the aforementioned silicon compound precursor can be completely hydrolyzed to more effectively show the subsequent gelation, aging, heating and fixation after the formation of the void structure.

In the present invention, the aforementioned silicon compound may, for example, be a hydrolyzate of trimethoxy(methyl)silane.

The above-mentioned monomeric silicon compound is not particularly limited, and for example, it can be appropriately selected according to the purpose of manufacturing the polysilicon porous body. In the manufacturing process of the aforementioned polysilicon porous body, for example, when low refractive index is emphasized, from the viewpoint of good low refractive index, the silicon compound is preferably the trifunctional silane; In the case of scratch resistance), based on the excellent scratch resistance, the aforementioned silicon compound is preferably the aforementioned tetrafunctional silane. In addition, for example, the silicon compound that is the raw material of the gel-like silicon compound may be used alone, or two or more kinds may be used in combination. As a specific example, the silicon compound may contain, for example, the trifunctional silane alone, the tetrafunctional silane alone, or both the trifunctional silane and the tetrafunctional silane, or may contain other silicon compounds. . When two or more silicon compounds are used as the aforementioned silicon compounds, the ratio is not particularly limited and can be set as appropriate.

The gelation of the silicon compound can be performed by, for example, a dehydration condensation reaction between the silicon compounds. The dehydration condensation reaction is preferably carried out in the presence of a catalyst, for example, the dehydration condensation catalyst such as an acid catalyst and an alkaline catalyst, the acid catalyst includes hydrochloric acid, oxalic acid, sulfuric acid, etc., the alkaline catalyst There are ammonia, potassium hydroxide, sodium hydroxide, ammonium hydroxide and so on. Aforementioned The dehydration condensation catalyst may be an acid catalyst or may be an alkaline catalyst, preferably an alkaline catalyst. In the dehydration condensation reaction, the amount of the catalyst added to the silicon compound is not particularly limited. For example, the catalyst is 0.1 to 10 moles, 0.05 to 7 moles, and 0.1 to 1 mole of the silicon compound. 5 moles.

The gelation of the aforementioned silicon compound is preferably carried out in a solvent, for example. The ratio of the aforementioned silicon compound in the aforementioned solvent is not particularly limited. Examples of the foregoing solvents include dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc), dimethylformamide (DMF), and γ- Butyrolactone (GBL), acetonitrile (MeCN), ethylene glycol ethyl ether (EGEE), etc. The aforementioned solvent may be, for example, one kind or a combination of two or more kinds. The solvent used for the aforementioned gelation is hereinafter also referred to as "a solvent for gelation".

The conditions for the aforementioned gelation are not particularly limited. The processing temperature of the solvent containing the silicon compound is, for example, 20 to 30°C, 22 to 28°C, and 24 to 26°C, and the processing time is, for example, 1 to 60 minutes, 5 to 40 minutes, and 10 to 30 minutes. When the aforementioned dehydration condensation reaction is performed, the processing conditions are not particularly limited, and the examples can be used. By performing the gelation, for example, the primary particles of the silicon compound can be grown by a siloxane bond, and then the primary particles are connected to each other in a bead shape as the reaction progresses to generate a three-dimensional gel.

The gel form of the gel-like silicon compound obtained in the gelation step is not particularly limited. "Gel" generally refers to a structure in which a solute has lost its independent mobility due to interaction and is in a solidified state. In addition, in the gel, the wet gel refers to the one containing the dispersion medium and the solute in the dispersion medium has the same structure, and the xerogel refers to the removal of the solvent. And the solute adopts the mesh structure with voids. In the present invention, the gel-like silicon compound is preferably a wet gel, for example. The residual amount of the silanol group of the gel-like silicon compound is not particularly limited, and for example, the range described below can be similarly exemplified.

The gel-like silicon compound produced by the gelation may be directly supplied to the pulverization step, for example, or may be subjected to a aging process in the aging step before the pulverization step. In the aging step, the conditions of the aging process are not particularly limited, for example, the gel-like silicon compound may be cultured in a solvent at a predetermined temperature. Through the aforementioned aging process, for example, for a gel-like silicon compound having a three-dimensional structure obtained by gelation, the primary particles can be further grown, thereby increasing the size of the particles themselves. Moreover, as a result, the contact state of the neck where the aforementioned particles are in contact with each other can be expanded from point contact to surface contact, for example. The gel-like silicon compound subjected to the aging process as described above, for example, increases the strength of the gel itself, and as a result, the strength of the three-dimensional basic structure of the crushed product after crushing can be further improved. Thus, when the coating film of the present invention is used to form a coating film, for example, the pore size of the void structure formed by the accumulation of the three-dimensional basic structure can be suppressed even in the drying step after coating. The solvent in the coating film evaporates and shrinks.

Among the temperatures of the aforementioned aging treatment, the lower limit is, for example, 30°C or higher, 35°C or higher, and 40°C or higher, the upper limit is, for example, 80°C or lower, 75°C or lower, 70°C or lower, and the range is, for example, 30 to 80°C or 35 ~75℃, 40~70℃. The aforementioned predetermined time is not particularly limited, and its lower limit is, for example, 5 hours or more, 10 hours or more, and 15 hours or more, its upper limit is, for example, 50 hours or less, 40 hours or less, 30 hours or less, and its range is, for example, 5 to 50 hours, 10~40 hours, 15~30 hours. In addition, the optimal conditions for aging are as described above, and it is desirable to set the conditions for obtaining an increase in the size of the primary particles of the gel-like silicon compound and an increase in the contact area of the neck. In addition, in the aforementioned aging step, the temperature of the aforementioned aging treatment should preferably take into consideration, for example, the boiling point of the solvent used. In the aging process, for example, when the aging temperature is too high, the solvent may be excessively volatilized, so that the pores of the three-dimensional void structure may be closed due to the concentration of the coating liquid and closed. On the other hand, when the ripening temperature is too low, for example, not only the aforementioned ripening effect cannot be sufficiently obtained, but also the temperature fluctuations over time in the mass production process will increase, which may result in products with poor quality.

For the aging treatment, for example, the same solvent as the gelation step can be used, and specifically, the reactant after the gel treatment (that is, the solvent containing the gel-like silicon) is preferably directly applied. The number of residual silanol groups contained in the gel-like silicon compound after the completion of gelation is, for example, alkane used as a raw material (such as the aforementioned silicon compound or its precursor) used in gelation The ratio of the residual silanol groups when the number of oxygen moles is 100 has a lower limit of, for example, 1% or less, 3% or less, and 5% or less, and an upper limit of, for example, 50% or more, 40% or more, and 30% or more, The range is, for example, 1-50%, 3-40%, and 5-30%. For the purpose of increasing the hardness of the gel-like silicon compound, for example, the lower the molar number of the remaining silanol group, the better. When the mole number of the remaining silanol groups is too high, for example, in forming the polysiloxane porous body, the void structure may not be maintained until the precursor before the polysiloxane porous body is crosslinked. On the other hand, when the mole number of residual silanol groups is too low, for example, the precursor of the polysiloxane porous body in the bonding step It may not be possible to perform cross-linking, and thus sufficient film strength cannot be imparted. In addition, the above description uses the residual silanol group as an example. In addition, for example, when a silicon compound modified with various reactive functional groups is used as the raw material of the gel-like silicon compound, the same phenomenon can be applied to each functional group. on.

In the present invention, the aforementioned pulverization step is the step for pulverizing the gel-like silicone compound as described above. The pulverization may be performed, for example, on the gel-like silicon compound (first coating material) after the gelation step, and may also be performed on the mature gel-like silicon compound (second coating material) that has been subjected to the aging process. Implementation.

The pulverization may, for example, directly pulverize the gelatinous silicon compound in the solvent for gelation, or may change the solvent for gelation to another solvent, and then the gelatinous silicon compound in the other solvent Perform crushing treatment. In addition, when the maturation step is performed on the gel-like silicon compound, it should be changed to another solvent in the following cases. For example, the catalyst and solvent used in the gelation step also remain after the maturation step, and then produce Gelation over time affects the pot life of the paint finally obtained, or causes a decrease in drying efficiency when the coating film formed using the aforementioned paint is dried. The aforementioned other solvents are also referred to as "pulverizing solvents" hereinafter.

For the pulverization, for example, the same solvent as the gelation step and the aging step may be used, or a solvent different from the gelation step and the aging step may be used. In the former case, for example, the aging step and the pulverization treatment may be directly performed on the reactant after the gelation step (for example, the gelation solvent containing the gel-like silicon compound). In addition, in the latter case, the reverse After applying the aging step directly to the application (for example, the gelling solvent containing the gelatinous silicon compound), change the gelation solvent to another solvent, and then apply the gelatinous silicon compound in the other solvent. Perform crushing treatment.

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

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 coating film formation described later.

The crushing method of the aforementioned gel-like silicon compound is not particularly limited, for example, it can be performed by the following devices: ultrasonic homogenizer, high-speed rotating homogenizer, other crushing devices using cavitation erosion, or oblique impact of liquids with high pressure The crushing device, etc. For example, a device such as a ball mill that pulverizes the medium physically destroys the void structure of the gel during pulverization. In contrast, the cavitation erosion pulverizing device preferred by the present invention such as a homogenizer is a medium-free method, so it is sheared at high speed. It is necessary to peel off the bonding surface of the weakly bonded silica particles that have been encapsulated in the three-dimensional structure of the gel. In this way, a completely new three-dimensional structure of sol can be obtained by crushing the aforementioned gel-like silicon compound, For example, the aforementioned three-dimensional structure can maintain a void structure with a certain 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 above-mentioned pulverization conditions are not particularly limited. For example, it is preferable to pulverize the gel in such a manner that the high-speed flow is imparted instantaneously without evaporating the solvent. For example, it is preferable to perform pulverization so as to become a pulverized product having a particle size deviation (for example, volume average particle size or particle size distribution) as described above. It is assumed that when the amount of work such as crushing time and strength is insufficient, not only may coarse particles remain and dense pores may not be formed, but also appearance defects may increase, and high quality may not be obtained. On the other hand, when the aforementioned workload is excessive, for example, sol particles that are finer than the desired particle size distribution may be formed, so that the pore size accumulated after coating and drying becomes finer, and the desired porosity cannot be satisfied.

After the above-mentioned pulverization step, the ratio of residual silanol groups contained in the pulverized material is not particularly limited. For example, it may be in the same range as exemplified in the gel-like silicon compound after the aging treatment.

After the pulverization step, the proportion of the pulverized material of the solvent containing the pulverized material is not particularly limited. For example, the relevant conditions of the coating of the present invention mentioned in the introduction can be exemplified. The ratio may be, for example, the condition of the solvent itself containing the pulverized product after the pulverization step, or the condition adjusted after the pulverization step before being used as the coating material.

The coating material of the present invention can be produced using the first coating material or the second coating material as described above. The first coating material contains the gel-like silicon compound as described above, and the gel-like silicon compound is made of a silicon compound containing at least 3 functional groups or less saturated bond functional groups. The manufacturing method of the first coating material includes, for example, a gelation step, which is to make the silicon compound in The gel-like silicon compound is gelated in the solvent, for example, the description of the gel-like silicon compound after the gelation step mentioned in the introduction can be used. The second coating raw material contains the gel-like silicon compound as described above, and the gel-like silicon compound is a gel-like substance made of a silicon compound containing at least a saturated bond functional group of at least 3 functions and has undergone aging treatment. The manufacturing method of the second coating raw material includes, for example, a aging step, which is to ripen the gel-like silicon compound prepared from the silicon compound in a solvent, for example, the gel-like silicon after the aging step mentioned in the introduction can be used Description of the compound.

In the above manner, the coating of the present invention can be produced, which contains the pulverized product of a gel-like silicon compound and a dispersion medium. In addition, a catalyst that can chemically bond the pulverized materials to each other in the aforementioned production steps or afterwards can also be added to the paint of the present invention. The amount of the catalyst added is not particularly limited, and it is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight with respect to the weight of the pulverized product of the gel-like silicon compound. With this catalyst, for example, the aforementioned pulverized substances can be chemically bonded to each other in a bonding step described later. The catalyst may be, for example, a catalyst for promoting cross-linking and bonding of the pulverized products. The chemical reaction for chemically combining the aforementioned pulverized products with each other preferably utilizes the dehydration condensation reaction of residual silanol groups contained in the silica sol molecules. The aforementioned catalyst promotes the reaction between the hydroxyl groups of the silanol group, and can achieve continuous film formation in which the void structure is hardened in a short time. Examples of the aforementioned catalyst include photoactive catalysts and thermally active catalysts. With the photoactive catalyst, for example, the pulverized materials can be chemically bonded to each other (eg, cross-linked bonding) without heating. Thereby, it is not easy to shrink due to heating, so a high porosity can be maintained. In addition to the aforementioned catalysts, catalyst-producing substances (catalysts) Generator) or replace it. For example, the catalyst may be a crosslinking reaction accelerator, and the catalyst generator may generate the crosslinking reaction accelerator. For example, in addition to the aforementioned photoactive catalyst, a substance (photocatalyst generator) that generates a catalyst by light may be used or replaced; or in addition to the aforementioned thermally active catalyst, a substance that generates a catalyst by heat ( Thermal catalyst generator) or replace it. The aforementioned photocatalyst generator is not particularly limited, and examples thereof include photobase generators (catalysts that generate alkaline catalysts by light irradiation), photoacid generators (substances that generate acidic catalysts by light irradiation), and the like, and The photobase agent is preferred. Examples of the aforementioned photobase generator include: 9-anthrylmethyl N,N-diethylcarbamate (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-( Anthraquinone-2-yl) ethyl imidazole carboxylate (1-(anthraquinon-2-yl) ethyl imidazole carboxylate, trade name WPBG-140), 2-nitrophenylmethyl 4-methacrylamide piperidine 1-Carboxylic acid ester (trade name WPBG-165), 1,2-diisopropyl-3-[bis(dimethylamino)methylene] 2-(3-benzoylphenyl)propan Ester (trade name WPBG-266), 1,2-dicyclohexyl-4,4,5,5-tetramethylbisguanidinium butyl triphenyl borate (trade name WPBG-300), and 2 -(9-oxadibenzopiperan-2-yl)propionic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene (Tokyo Chemical Industry Co., Ltd.), containing 4- Piperidine methanol compound (trade name HDPD-PB100: manufactured by Heraeus), etc. In addition, the aforementioned trade names containing "WPBG" are the trade names of Wako Pure Chemical Industries, Ltd. Examples of the aforementioned photoacid generators include aromatic osmium salts (trade name SP-170: ADEKA Corporation) and triaryl osmium salts (trade name) CPI101A: San-Apro Ltd.), aromatic tungsten salt (trade name Irgacure250: Ciba Japan K.K.), etc. In addition, the catalyst that chemically bonds the pulverized products with each other is not limited to the photoactive catalyst and the photocatalyst generating agent, and may be, for example, a thermally active catalyst or a thermal catalyst generating agent such as urea. Examples of catalysts that chemically bond the pulverized products to each other include alkaline catalysts such as potassium hydroxide, sodium hydroxide, and ammonium hydroxide, and acid catalysts such as hydrochloric acid, acetic acid, and oxalic acid. Among these, alkaline catalysts are preferred. The catalyst that chemically combines the pulverized products with each other can be added to the sol particle liquid (for example, suspension) containing the pulverized product just before coating, or it can be prepared that the catalyst has been mixed to Use a mixture of solvents. The mixed liquid may be, for example, a coating liquid directly added to the sol particle liquid, a solution in which the catalyst is dissolved in a solvent, or a dispersion liquid in which the catalyst is dispersed in a solvent. The aforementioned solvent is not particularly limited, and examples thereof include various organic solvents, water, and buffer solutions.

In addition, for example, it is possible to add a crosslinking auxiliary agent to indirectly bond the pulverized substances of the gel-like silicon compound to the coating of the present invention. The cross-linking auxiliary agent can enter into the particles (the aforementioned crushed material), and use the interaction or combination of the particles and the cross-linking auxiliary agent, so that the particles that are slightly separated in distance can also be combined with each other, which can be effectively Increase strength. The aforementioned cross-linking auxiliary agent is preferably a multi-cross-linked silane monomer. The aforementioned multi-crosslinked silane monomer specifically has, for example, 2 or more and 3 or less alkoxysilyl groups, and the chain length between the alkoxysilyl groups may be carbon number 1 or more and 10 or less, and may contain elements other than carbon . Examples of the aforementioned cross-linking auxiliary agent include: bis(trimethoxysilyl)ethane, bis(triethoxysilyl)ethane, bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis (Triethoxysilyl) propane, bis (trimethoxysilyl) propane, bis (triethoxy Silyl) butane, bis (trimethoxysilyl) butane, bis (triethoxysilyl) pentane, bis (trimethoxysilyl) pentane, bis (triethoxysilyl) hexane, bis (triethoxysilyl) hexane Trimethoxysilyl)hexane, bis(trimethoxysilyl)-N-butyl-N-propyl-ethane-1,2-diamine, ginseng-(3-trimethoxysilylpropyl) trimer Isocyanate, ginseng-(3-triethoxysilylpropyl) trimer isocyanate, etc. The addition amount of the cross-linking 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 with respect to the weight of the pulverized product of the silicon compound.

[2. How to use paint]

As a method for using the paint of the present invention, the following is an example of a method for manufacturing a polysilicon porous body, but the present invention is not limited thereto. In addition, the polysiloxane porous body manufactured using the coating material of the present invention may be hereinafter referred to as "polysiloxane porous body of the present invention".

The manufacturing method of the aforementioned polysiloxane porous body is characterized by, for example, comprising: a precursor forming step, which uses the coating of the present invention to form the polysiloxane porous body precursor; and a bonding step, which causes the precursor The aforementioned pulverized materials containing the aforementioned paint are chemically combined with each other. The aforementioned precursor may be, for example, a coating film.

According to the aforementioned method for manufacturing a polysilicon porous body, a porous structure that can perform the same function as the air layer can be formed, for example. The reason is presumed as follows, but the present invention is not limited by this presumption.

Since the coating material of the present invention used in the manufacturing method of the polysiloxane porous body contains the pulverized product of the gel-like silicon compound, the three-dimensional structure of the gel-like silicone compound is dispersed into a three-dimensional basic structure. Therefore, in the manufacturing method of the aforementioned polysilicon porous body, for example If the precursor is used to form the precursor (for example, a coating film), the three-dimensional basic structure is accumulated to form a void structure mainly composed of the three-dimensional basic structure. That is, a completely new three-dimensional structure formed by the pulverized product of the three-dimensional basic structure and completely different from the three-dimensional structure of the gel-like silicon compound can be formed according to the method of manufacturing the polysilicon porous body. In addition, in the method for manufacturing the polysilicon porous body, in order to further chemically combine the pulverized products, the new three-dimensional structure is fixed. Therefore, although the porous polysiloxane body manufactured according to the manufacturing method of the porous polysiloxane body has a structure with voids, it can still maintain sufficient strength and flexibility. The polysilicon porous body prepared by the present invention can be used as a member using voids for products in a wide range of fields, such as heat insulating materials, sound absorbing materials, optical members, and ink image receiving layers, etc., and can be manufactured with various functions. Laminated film.

The above-mentioned method for manufacturing the polysilicon porous body can be described using the coating of the present invention unless otherwise specified.

In the step of forming the precursor of the porous body, for example, the coating material of the present invention is applied to the substrate. For example, the coating of the present invention can be applied to a substrate and the coating film is dried, and then the pulverized materials are chemically combined with each other (eg, cross-linked) through a bonding step, and the continuous film formation has a certain degree or more Vapour layer of membrane strength.

The coating amount of the coating material with respect to the substrate is not particularly limited, and for example, it can be appropriately set according to the desired thickness of the porous polysiloxane body. As a specific example, when forming the polysilicon porous body with a thickness of 0.1 to 1000 μm, the coating amount of the coating material with respect to the substrate is within an area of 1 m ² of the substrate, for example, the pulverized product is 0.01 to 60,000 μg , 0.1~5000μg, 1~50μg. The ideal coating amount of the aforementioned coating is related to, for example, the liquid concentration or the coating method, so it is difficult to make a single definition. In consideration of productivity, it is better to apply a thin layer as much as possible. When the coating amount is too large, for example, the possibility of being dried in a drying furnace before the solvent volatilizes increases. In this way, before the nano-pulverized sol particles settle and accumulate in the solvent to form a void structure, the formation of void structure may be hindered by the drying of the solvent, which greatly reduces the void ratio. On the other hand, when the coating amount is too thin, the risk of coating cissing may be greatly increased due to unevenness of the substrate, deviation in hydrophilicity and hydrophobicity, and the like.

After the coating material is applied to the substrate, the precursor of the porous body (coating film) may be dried. The purpose of the drying process is not only to remove the solvent (the solvent contained in the paint) in the precursor of the porous body, but also to settle and accumulate sol particles during the drying process to form a void structure. The temperature of the drying process is, for example, 50 to 250°C, 60 to 150°C, and 70 to 130°C, and the time of the drying process is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, and 0.3 to 3 minutes. Regarding the drying treatment temperature and time, for example, in terms of continuous productivity or high porosity, lower temperature and shorter time are preferred. If the conditions are excessively severe, for example, when the substrate is a resin film, when the glass transition temperature of the substrate is approached, the substrate will stretch in the drying furnace and may have a void structure formed immediately after coating There are shortcomings such as cracks. On the other hand, if the condition is too loose, for example, because it contains residual solvent at the time of leaving the drying furnace, it may cause appearance defects such as mixing and scratching when rubbing with the roller in the next step.

The aforementioned drying treatment may be, for example, natural drying, heating drying, or reduced-pressure drying. The aforementioned drying method is not particularly limited, and for example, a general heating mechanism can be used. Examples of the heating mechanism include a hot air heater, a heating roller, and a far-infrared heater. Among them, heating and drying should be used on the premise of continuous industrial production. Regarding the usable solvents, when the purpose is to suppress the shrinkage stress caused by the solvent volatilization during drying and the subsequent cracking of the void layer (the aforementioned polysiloxane porous body), the solvent with low surface tension is used good. Examples of the aforementioned solvent include lower alcohols represented by isopropyl alcohol (IPA), hexane, and perfluorohexane, but are not limited thereto. In addition, for example, a small amount of perfluoro-based surfactant or silicon-based surfactant may be added to the IPA or the like to reduce the surface tension.

The aforementioned substrate is not particularly limited. For example, thermoplastic resin substrates, glass substrates, inorganic substrates represented by silicon, plastics and semiconductors molded with thermosetting resins, and carbon nanotubes are suitable. The representative carbon fiber materials are not subject to these restrictions. Examples of the shape of the aforementioned substrate include films and thin plates. Examples of the aforementioned thermoplastic resin include polyethylene terephthalate (PET), acrylic acid, cellulose acetate propionate (CAP), cycloolefin polymer (COP), triacetate (TAC), and polynaphthalene dicarboxylic acid. Ethylene glycol (PEN), polyethylene (PE), polypropylene (PP), etc.

In the method for manufacturing the polysilicon porous body, the bonding step is a step for chemically bonding the pulverized materials contained in the precursor (coating film) of the porous body. By the aforementioned bonding step, for example, the three-dimensional structure of the pulverized product in the precursor of the porous body can be fixed. When fixing by conventional sintering, for example, it is carried out at a temperature of 200°C or higher Warm treatment stimulates the dehydration condensation of silanol groups to form siloxane bonds. In the aforementioned bonding step of the present invention, for example, when the substrate is a resin film, by reacting various additives that catalyze the above-mentioned dehydration condensation reaction, the aforementioned substrate will not be damaged, and it can also be dried at a low temperature around 100°C. The temperature and the short processing time of only a few minutes continuously form and fix the void structure.

The method of chemical bonding is not particularly limited. For example, it can be appropriately determined according to the type of the gel-like silicon compound. As a specific example, the chemical bonding may be performed by chemical cross-linking between the pulverized products. For example, when inorganic particles such as titanium oxide are added to the pulverized product, the inorganic particles may also be considered. Chemical cross-linking with the aforementioned crushed material. In addition, in the case of providing biological catalysts such as enzymes, it is also possible to chemically cross-link and combine the other sites different from the active sites of the catalyst with the pulverized material. Therefore, the present invention is not only like a void layer (polysilicon porous body) formed by the aforementioned sol particles, but can also be extended to organic-inorganic hybrid void layers, host-guest void layers, etc. limited.

The aforementioned bonding step can be performed by a chemical reaction in the presence of a catalyst, for example, in accordance with the type of the pulverized product of the aforementioned gel-like silicon compound. The chemical reaction of the present invention preferably utilizes the dehydration condensation reaction of the residual silanol group contained in the pulverized product of the aforementioned gel-like silicon compound. The aforementioned catalyst promotes the reaction of the hydroxyl groups of the silanol groups with each other, so that the continuous film formation of the void structure can be hardened in a short time. Examples of the aforementioned catalyst include alkaline catalysts such as potassium hydroxide, sodium hydroxide, and ammonium hydroxide, and acid catalysts such as hydrochloric acid, acetic acid, and oxalic acid, but are not limited thereto. The catalyst for the aforementioned dehydration condensation reaction is preferably an alkaline catalyst. In addition, it is also suitable to use light that exhibits catalytic activity by irradiation with light (for example, ultraviolet rays) Acid generating catalyst, photobase generating catalyst, photoacid generator, photobase generator, etc. The photoacid generating catalyst, photobase generating catalyst, photoacid generating agent and photobase generating agent are not particularly limited, as described above. The aforementioned catalyst is as described above, and is preferably added to the sol particle liquid containing the pulverized material just before coating or used as a mixed solution in which the aforementioned catalyst is mixed in a solvent. The mixed liquid may be, for example, a coating liquid directly added to the sol particle liquid, a solution in which the catalyst is dissolved in a solvent, or a dispersion liquid in which the catalyst is dispersed in a solvent. The aforementioned solvent is not particularly limited, and as mentioned above, for example, water, buffer, etc. may be mentioned.

The chemical reaction in the presence of the catalyst can be carried out by, for example, irradiating or heating the coating film containing the catalyst and the catalyst has been previously added to the coating; or the coating The film is irradiated with light or heated after spraying the catalyst; or it is irradiated with light or heated while spraying the catalyst. For example, when the catalyst is a photoactive catalyst, the pulverized materials can be chemically combined with each other by light irradiation to form the polysilicon porous body. In addition, when the catalyst is a thermally active catalyst, the pulverized materials can be chemically combined with each other by heating to form the polysilicon porous body. The light irradiation amount (energy) of the aforementioned light irradiation is not particularly limited, and it is, for example, 200 to 800 mJ/cm ² , 250 to 600 mJ/cm ^2, or 300 to 400 mJ/cm ² in @360nm conversion. In order to prevent the decomposition of the light absorption by the catalyst generator from progressing due to insufficient irradiation amount and failing to achieve good results, a cumulative light amount of 200 mJ/cm ² or more is suitable. In addition, in order to prevent the substrate under the void layer from being damaged and generating thermal wrinkles, the accumulated light amount of 800 mJ/cm ² or less is suitable. The conditions of the heat treatment are not particularly limited. 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, and 0.3 to 3 minutes. In addition, as for the usable solvent, for example, when the purpose is to suppress shrinkage stress caused by the solvent volatilization during drying and subsequent cracking of the void layer, a solvent with low surface tension is preferred. Examples include: lower alcohols such as isopropyl alcohol (IPA), hexane, and perfluorohexane, but are not limited to these.

The polysilicon porous body of the present invention can be manufactured in the above manner, but the manufacturing method of the present invention is not limited thereto.

In addition, the obtained polysilicone porous body of the present invention may be subjected to a strength increasing step (for example, hereinafter referred to as a "curing step") such as heat curing to increase the strength. For example, when the polysilicon porous body of the present invention is laminated on a resin film, the adhesive peel strength with respect to the resin film can be increased by the aforementioned strength-raising step (aging step). In the aforementioned strength-raising step (mature step), for example, the polysiloxane porous body of the present invention may also be heated. The temperature of the aforementioned aging step is, for example, 40 to 80°C, 50 to 70°C, and 55 to 65°C. The aforementioned reaction time is, for example, 5 to 30 hr, 7 to 25 hr, or 10 to 20 hr. In the aging step, for example, by setting the heating temperature to a low temperature, the shrinkage of the polysiloxane porous body can be suppressed and the adhesive peel strength can be improved at the same time, achieving both high void ratio and strength.

The phenomenon and mechanism of germination in the aforementioned strength-raising step (maturation step) are unknown, and we believe that it is because, for example, by the catalyst contained in the polysilicon porous body of the present invention, the aforementioned pulverized materials are chemically combined with each other (for example, cross-linking) Reaction) further development to increase strength. As a specific example, when there is a residual silanol group (OH group) in the polysiloxane porous body, it is the residual silane Alcohol groups chemically bond with each other through a cross-linking reaction. In addition, the catalyst contained in the polysilicon porous body of the present invention is not particularly limited. For example, it may be the catalyst used in the aforementioned bonding step, and may be the photobase generator used in the aforementioned bonding step. The alkaline substance generated by the irradiation may be an acid substance generated by light irradiation of the photoacid generating catalyst used in the aforementioned bonding step. However, this description is only an example and does not limit the present invention.

In addition, an adhesive layer can also be further formed on the polysilicon porous body of the present invention (adhesive layer forming step). Specifically, for example, the adhesive layer may be formed by coating (coating) an adhesive or an adhesive on the polysilicon porous body of the present invention. In addition, the adhesive layer side of the adhesive tape and the like on which the adhesive layer is laminated on the base material may be attached to the polysilicon porous body of the present invention, thereby forming on the polysilicon porous body of the present invention The aforementioned adhesive layer. At this time, the base material such as the adhesive tape can be maintained in the state of being bonded thereon, and can also be peeled from the adhesive layer. In the present invention, "adhesive" and "adhesive layer" refer to, for example, an agent or layer that is premised on the re-peeling of the adherend. In the present invention, "adhesive" and "adhesive layer" mean, for example, an agent or layer that does not presuppose the re-peeling of the adherend. However, in the present invention, "adhesive" and "adhesive" are not clearly distinguishable, nor are "adhesive layer" and "adhesive layer". In the present invention, the adhesive or adhesive that forms the adhesive layer is not particularly limited, and for example, a general adhesive or adhesive can be used. Examples of the adhesive or the adhesive include acrylic-based, vinyl alcohol-based, polysiloxane-based, polyester-based, polyurethane-based, and polyether-based polymer adhesives and rubber-based adhesives. In addition, a water-soluble cross-linking agent composed of a vinyl alcohol polymer such as glutaraldehyde, melamine, oxalic acid, etc. The agent waits. Only one type of these adhesives and adhesives may be used, or plural types may be used in combination (eg, mixing, lamination, etc.). The thickness of the aforementioned adhesive layer is not particularly limited, for example, it is 0.1-100 μm, 5-50 μm, 10-30 μm, or 12-25 μm.

In addition, the polysilicon porous body of the present invention can be reacted with the adhesive layer to form an intermediate layer disposed between the polysilicon porous body of the present invention and the adhesive layer (intermediate layer forming step). With the intermediate layer, for example, the polysilicon porous body of the present invention is not easily peeled off from the adhesive layer. The reason (mechanism) is unknown, presumably because of the anchoring property (anchoring effect) of the aforementioned intermediate layer. The anchoring property (anchoring effect) refers to a phenomenon (effect) in which the intermediate layer has a structure embedded in the void layer in the vicinity of the interface between the void layer and the intermediate layer, so that the interface is firmly fixed. However, the reason (mechanism) is only an example of speculative reason (mechanism), and the present invention cannot be limited. The reaction between the porous polysilicon body of the present invention and the aforementioned adhesive layer is not particularly limited, and may be, for example, a reaction by a catalyst. The aforementioned catalyst may be, for example, the catalyst contained in the polysilicon porous body of the present invention. Specifically, it may be, for example, the catalyst used in the aforementioned bonding step, or may be the alkaline substance generated by light irradiation of the photobase generating catalyst used in the aforementioned bonding step, or may be the aforementioned substance in the aforementioned bonding step The photoacid generation catalyst used is an acidic substance produced by light irradiation. In addition, the reaction between the porous polysilicon body of the present invention and the aforementioned adhesive layer may be, for example, a reaction that can generate a new chemical bond (for example, a cross-linking reaction). The temperature of the aforementioned 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. In addition, the step of forming the intermediate layer can also serve to enhance The aforementioned strength improvement step (maturation step) of the strength of the polysilicon porous body of the present invention.

The polysilicon porous body of the present invention produced in the above-mentioned manner can be further laminated with other thin films (layers) to form a laminated structure containing the aforementioned porous structure. At this time, in the aforementioned laminated structure, for example, each constituent element may be laminated by an adhesive or an adhesive.

Based on efficiency, the lamination of each of the aforementioned constituent elements can be carried out by continuous processing using a long film (so-called roll to roll, etc.). When the substrate is a molded product or element, etc. Those who have been processed in batches will be stacked.

The method for forming the polysiloxane porous body on the substrate by using the coating material of the present invention will be described below with reference to FIGS. 1-3. Figure 2 shows the steps of attaching the protective film and winding it after manufacturing the aforementioned polysilicon porous body. The above method can also be used when laminating another functional film, or another function can be applied After the film is dried, the polysilicone porous body after the film formation is attached just before being wound up. In addition, the film-making method shown in the figure is only an example and is not limited by these.

In the cross-sectional view of FIG. 1, an example of the steps of the method of forming the polysiloxane porous body on the substrate is schematically shown. In FIG. 1, the method for forming the polysilicon porous body includes: a coating step (1), which is to apply the aforementioned coating material 20" of the present invention on the substrate 10; a coating film forming step (drying step) (2 ), the coating 20" is dried to form a coating film 20', the coating film 20' is the precursor layer of the aforementioned polysilicon porous body; and a chemical treatment step (for example, a cross-linking treatment step) (3), which is The coating film 20' is formed by chemical treatment (for example, cross-linking treatment) 聚silicon porous body 20. In this way, as shown in the figure, the polysilicon porous body 20 can be formed on the substrate 10. In addition, the method for forming the polysilicon porous body may or may not include steps other than the steps (1) to (3).

In the foregoing coating step (1), the coating method of the coating 20" is not particularly limited, and a general coating method can be used. The foregoing coating method can be exemplified by a slot die coating method, reverse 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 , Flexo printing method, wire bar coating method, spray coating method, extrusion coating method, curtain coating method, reverse coating method, etc. Among these, based on productivity, smoothness of the coating film, etc. , Preferably extrusion coating method, curtain coating method, roll coating method, micro gravure coating method, etc. The coating amount of the aforementioned coating 20" is not particularly limited, for example, a porous structure (polysilicon The oxygen porous body) 20 is appropriately set so as to have an appropriate thickness. The thickness of the porous structure (polysilicon porous body) 20 is not particularly limited, and may be as described above.

In the aforementioned drying step (2), the paint 20" is dried (i.e., the dispersion medium contained in the paint 20" is removed) to form a coating film (precursor layer) 20'. The conditions of the drying process are not particularly limited, as described above.

In addition, in the aforementioned chemical treatment step (3), the coating film 20' containing the aforementioned catalyst (for example, a photoactive catalyst or a thermally active catalyst such as KOH) added before coating is subjected to light irradiation or heating, The aforementioned pulverized materials in the coating film (precursor) 20' are chemically bonded to each other (for example, cross-linked) to form the polysilicon porous body 20. The light irradiation or heating conditions of the aforementioned chemical treatment step (3) are not particularly limited, just like the aforementioned.

Next, FIG. 2 schematically shows an example of a slit die coating method coating apparatus and a method for forming the aforementioned polysilicon porous body. In addition, although FIG. 2 is a cross-sectional view, hatching is omitted for legibility.

As shown in the figure, each step of the method of using the device is carried out while the substrate 10 is conveyed in one direction by a roller. The conveying speed is not particularly limited, and is, for example, 1 to 100 m/min, 3 to 50 m/min, and 5 to 30 m/min.

First, the substrate 10 is conveyed while being spun out from the feed roller 101, and after the coating roller 102 performs the coating step (1), it is then moved to the drying step (2) in the oven zone 110. The foregoing coating step ( 1) The coating 20 of the present invention is coated on the substrate 10. In the coating device 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 After heating, it is performed at room temperature. In the drying step (2), the heating mechanism 111 is used. As mentioned above, the heating mechanism 111 can suitably use a hot air heater, a heating roller, a far-infrared heater, etc. Also, for example, the drying Step (2) is divided into multiple steps, so that the drying temperature becomes higher and higher with subsequent drying steps.

After the drying step (2), the chemical treatment step (3) is performed in the chemical treatment zone 120. In the chemical treatment step (3), for example, when the dried coating film 20' contains a photoactive catalyst, a lamp (light irradiation mechanism) 121 arranged above and below the base material 10 is used for light irradiation. Alternatively, for example, when the coating film 20 ′ after drying contains a thermally active catalyst, a hot air heater (heating mechanism) is used instead of the lamp (light irradiation device) 121, and the base material 10 is replaced by a hot air heater 121 disposed above and below the base material 10 heating. By this cross-linking treatment, the chemical bonding of the aforementioned pulverized substances in the coating film 20' can be initiated, and the porous polysiloxane 20 can be hardened and strengthened. Then, after the chemical treatment step (3), the substrate 10 is wound up by the winding roller 105 The laminated body of the polysilicon porous body 20. In addition, in FIG. 2, the porous structure 20 of the laminate is covered and protected by a protective sheet unscrewed by the roller 106. Here, another layer formed of a long film may be laminated on the porous structure 20 instead of the protective sheet.

FIG. 3 schematically shows an example of a coating apparatus of a micro gravure method (micro gravure coating method) and a method for forming the aforementioned porous structure. In addition, although the figure is a cross-sectional view, hatching is omitted for legibility.

As shown in the figure, each step of the method of using the device is carried out at the same time as the base material 10 is transported in one direction by a roller as in FIG. 2. The conveying speed is not particularly limited, and is, for example, 1 to 100 m/min, 3 to 50 m/min, and 5 to 30 m/min.

First, the substrate 10 is conveyed while being spun out from the feed roller 201, and the coating step (1) is performed, which applies the coating 20" of the present invention on the substrate 10. The coating 20" is applied as shown in the figure. The liquid storage area 202, doctor knife 203 and microgravure 204 are used. Specifically, the paint 20 ″ stored 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 and coated on the surface of the substrate 10 with the micro-gravure plate 204 at the same time. In addition, the micro-gravure plate 204 For example, without being limited to this, any other coating mechanism may be used.

Next, the drying step (2) is performed. Specifically, as shown in the figure, the substrate 10 coated with the paint 20" is transported in the oven zone 210 and heated and dried by the heating mechanism 211 in the oven zone 210. The heating mechanism 211 may also be the same as FIG. 2, for example. For example, by dividing the oven zone 210 into a plurality of blocks, the drying step (2) can be divided into a plurality of steps, so that the drying temperature is followed by subsequent drying The dry steps are getting higher and higher. After the drying step (2), the chemical treatment step (3) is performed in the chemical treatment zone 220. In the chemical treatment step (3), for example, when the dried coating film 20' contains a photoactive catalyst, a lamp (light irradiation mechanism) 221 disposed above and below the base material 10 is used for light irradiation. Or, for example, when the dried coating film 20' contains a thermally active catalyst, a hot air heater (heating mechanism) will be used instead of the lamp (light irradiation device) 221 to arrange the hot air heater (heating mechanism) below the base material 10 ) 221 The base material 10 is heated. By this cross-linking treatment, the chemical bonding of the pulverized materials in the coating film 20' can be excited to form the polysilicon porous body 20.

Then, after the chemical treatment step (3), the laminate having the polysilicon porous body 20 formed on the base material 10 is wound up by the winding roller 251. Thereafter, another layer may be laminated on the above-mentioned laminate. In addition, before winding up the layered body by the winding roller 251, another layer may be layered on the layered volume.

In addition, FIGS. 4 to 6 show another example of the continuous processing steps of the method for forming the polysilicon porous body of the present invention. As shown in the cross-sectional view of FIG. 4, this method is to perform the strength improvement step (maturation step) (4) after the chemical treatment step (for example, cross-linking treatment step) (3) to form the polysilicon porous body 20, and otherwise The methods shown in Figures 1 to 3 are the same. As shown in FIG. 4, in the strength increasing step (mature step) (4), the strength of the polysilicon porous body 20 is increased to produce a polysilicon porous body 21 with enhanced strength. The strength improvement step (aging step) (4) is not particularly limited, as described in the introduction.

FIG. 5 is a schematic diagram showing another example of a coating apparatus different from the slit die coating method of FIG. 2 and the aforementioned method of forming a polysilicon porous body using the same. As shown in the figure, the coating device performs the chemical treatment step (3) The chemical treatment area 120 is immediately followed by an intensity enhancement area (maturation area) 130 for performing the intensity enhancement step (maturation step) (4), except that it is the same as the device of FIG. 2. That is, after the chemical treatment step (3), a strength-raising step (curing step) (4) is performed in the strength-raising zone (curing zone) 130 to increase the adhesive peel strength of the polysilicon porous body 20 with respect to the resin film 10, and A polysilicon porous body 21 with enhanced adhesive peel strength is formed. The strength improvement step (aging step) (4) can also be performed by heating the polysilicon porous body 20 in the aforementioned manner using, for example, a hot air heater (heating mechanism) 131 disposed above and below the base material 10. The heating temperature, time, etc. are not particularly limited, as described in the introduction. Thereafter, as in FIG. 3, the laminated film on which the polysilicon porous body 21 is formed on the base material 10 is wound up by the winding roller 105.

6 is a schematic diagram showing another example of a coating apparatus different from the micro gravure method (micro gravure coating method) of FIG. 3 and the aforementioned porous structure forming method using the same. As shown in the figure, the coating device immediately after the chemical treatment zone 220 of the chemical treatment step (3) has the strength improvement zone (maturation zone) 230 for performing the strength improvement step (maturation step) (4), and otherwise The device in Figure 3 is the same. That is, after the chemical treatment step (3), a strength-raising step (curing step) (4) is performed in the strength-raising area (curing area) 230 to increase the adhesive peel strength of the polysilicon porous body 20 with respect to the resin film 10, and A polysilicon porous body 21 with enhanced adhesive peel strength is formed. The strength improvement step (aging step) (4) can also be performed by heating the polysilicon porous body 20 in the manner described above, for example, using a hot air heater (heating mechanism) 231 arranged above and below the base material 10. The heating temperature, time, etc. are not particularly limited, as described in the introduction. Thereafter, in the same way as in FIG. 3, the polysilicon porous is formed on the base material 10 by the winding roller 251 The laminated film of the body 21.

7 to 9 show another example of the continuous processing steps of the method for forming the polysilicon porous body of the present invention. As shown in the cross-sectional view of FIG. 7, after the chemical treatment step (for example, the cross-linking treatment step) (3) of forming the polysilicon porous body 20, the method includes: coating the adhesive layer 30 on the polysilicon porous body 20 Adhesive layer coating step (adhesive layer forming step) (4), and intermediate layer forming step (5) for reacting polysilicon porous body 20 with adhesive layer 30 to form intermediate layer 22. Except for these, the method in Figures 7-9 is the same as the method shown in Figures 4-6. In addition, in FIG. 7, the intermediate layer forming step (5) also serves as a step (strength improvement step) to increase the strength of the polysilicon porous body 20, and after the intermediate layer forming step (5), the polysilicon porous body 20 is promoted It is a polysilicon porous body 21 with enhanced strength. However, the present invention is not limited to this, for example, the polysilicon porous body 20 may not be changed after the intermediate layer forming step (5). The adhesive layer coating step (adhesive layer forming step) (4) and the intermediate layer forming step (5) are not particularly limited, as described in the introduction.

FIG. 8 is a schematic diagram showing yet another example of a slit die coating method coating device and a method for forming the aforementioned polysiloxane porous body using the same. As shown in the figure, the coating device has the adhesive layer coating area 130a for performing the adhesive layer coating step (4) immediately after the chemical processing area 120 for performing the chemical processing step (3). The device is the same. In the same figure, the intermediate layer forming area (curing area) 130 arranged immediately behind the adhesive layer coating area 130a can be strengthened by the hot air heater (heating mechanism) 131 arranged above and below the base material 10, as shown in FIG. The lifting zone (mature zone) 130 is subjected to the same heat treatment. That is, in the device of FIG. 8, the adhesive layer is applied after the chemical treatment step (3) The coating step (adhesive layer forming step) (4), that is, applying (coating) an adhesive or an adhesive on the polysilicon porous body 20 by the adhesive layer coating mechanism 131a in the adhesive layer coating region 130a Then, the adhesive layer 30 is formed. Furthermore, as described above, it is also possible to attach (attach) an adhesive tape or the like with the adhesive layer 30 instead of applying (coating) an adhesive or an adhesive. Next, an intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming area (matured area) 130 to react the polysilicon porous body 20 with the adhesive layer 30 to form the intermediate layer 22. Also, as described above, in this step, the polysilicon porous body 20 becomes a polysilicon porous body 21 with enhanced strength. The heating temperature, time, etc. using the hot air heater (heating mechanism) 131 are not particularly limited, as described in the introduction.

9 is a schematic diagram showing yet another example of a coating apparatus of a micro gravure method (micro gravure coating method) and a method of forming the aforementioned porous structure using the same. As shown in the figure, the coating device has the adhesive layer coating area 230a for performing the adhesive layer coating step (4) immediately after the chemical processing area 220 for performing the chemical processing step (3). The device is the same. In the same figure, the intermediate layer forming region (curing region) 230 disposed immediately behind the adhesive layer coating region 230a can be strengthened as shown in FIG. 6 by the hot air heater (heating mechanism) 231 disposed above and below the substrate 10 The lifting zone (mature zone) 230 has the same heat treatment. That is, in the device of FIG. 9, the adhesive layer coating step (adhesive layer forming step) (4) is performed after the chemical treatment step (3), that is, by the adhesive layer in the adhesive layer coating area 230a The coating mechanism 231 a coats (coats) an adhesive or an adhesive on the polysilicon porous body 20 to form an adhesive layer 30. Furthermore, as described above, it is also possible to attach (attach) an adhesive tape or the like with the adhesive layer 30 instead of applying (coating) an adhesive or an adhesive. Come again, The intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming area (matured area) 230 to react the polysilicon porous body 20 with the adhesive layer 30 to form the intermediate layer 22. Also, as described above, in this step, the polysilicon porous body 20 becomes a polysilicon porous body 21 with enhanced strength. The heating temperature, time, etc. using the hot air heater (heating mechanism) 231 are not particularly limited, as described in the introduction.

[3. Polysilicon porous body]

The polysilicon porous body of the present invention is characterized in that the scratch resistance obtained by using Bemcot (registered trademark) is 60 to 100%, as shown below, and the number of folding endurance obtained by using the MIT test is 100 times. Above, but not limited to this.

The polysilicone porous system of the present invention uses the pulverized product of the gel-like silicon compound, so the three-dimensional structure of the gel-like silicon compound has been broken to form a brand-new three-dimensional structure completely different from the gel-like silicon compound. In this way, the polysilicon porous body of the present invention can be formed into a layer with a new pore structure (new void structure) that cannot be obtained from the layer formed of the aforementioned gel-like silicon compound, thereby forming a high void ratio Porous silica porous body on the meter scale. In addition, the porous polysiloxane system of the present invention, for example, adjusts the number of siloxane bond functional groups of the gel-like silicon compound to chemically bond the pulverized products with each other. In addition, after forming a new three-dimensional structure as a precursor of the aforementioned polysiloxane porous body, chemical bonding (eg, crosslinking) is performed in the bonding step. Therefore, although the polysiloxane porous body of the present invention has a void structure, it can still maintain sufficient Strength and flexibility. Therefore, according to the present invention, the polysilicon porous body can be easily and simply supplied to various objects. Specifically, this The polysilicon porous body of the invention can be used as a heat insulating material, a sound absorbing material, a stent material for regenerative medicine, an anti-condensation material, an optical member, etc. in place of the air layer, for example.

The polysilicon porous body of the present invention is, for example, the aforementioned crushed product generally containing a gel-like silicon compound, and the crushed products are chemically combined with each other. In the polysilicon porous body of the present invention, the form of the chemical bond (chemical bond) between the pulverized products is not particularly limited, and specific examples of the chemical bond include cross-linked bonds. In addition, the method of chemically combining the aforementioned pulverized materials with each other is as described in detail in the aforementioned method for manufacturing the polysiloxane porous body.

The aforementioned cross-linking bond is, for example, a siloxane bond. Examples of the siloxane bond include T2 bond, T3 bond, and T4 bond shown below. When the polysiloxane porous body of the present invention has a siloxane bond, for example, it may have any one kind of bond, any two kinds of bonds, or all three kinds of bonds. In the aforementioned siloxane bond, the more the ratio of T2 and T3, the more flexible, the more the original characteristics of the gel can be expected, but the strength will be weaker. On the other hand, if the T4 ratio in the aforementioned siloxane bond is large, although the film strength tends to be expressed, the size of the gap becomes smaller and the flexibility becomes weaker. Therefore, it is appropriate to change the ratio of T2, T3, and T4 according to, for example, use.

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

In addition, the polysiloxane porous body of the present invention preferably has, for example, a silicon atom contained in a siloxane-bonded state. As a specific example, the ratio of unbonded silicon atoms (that is, residual silanol) in the total silicon atoms contained in the porous polysilicon body is, for example, less than 50%, 30% or less, and 15% or less.

The polysilicon porous body of the present invention has a pore structure, and the pore size of the pore refers to the aforementioned major axis diameter of the major axis diameter and the minor axis diameter of the void (pore). The ideal pore size is, for example, 5 nm to 200 nm. In the aforementioned void size, the lower limit is, for example, 5 nm or more, 10 nm or more, and 20 nm or more, and the upper limit is, for example, 1000 μm or less, 500 μm or less, and 100 μm or less, and the range is, for example, 5 nm to 1000 μm, 10 nm to 500 μm, and 20 nm to 100 μm. The gap size is to determine the appropriate gap size according to the purpose of using the gap structure, for example, it must be adjusted to the desired gap size according to the purpose. In addition, the gap size can be evaluated by the following method, for example.

(Evaluation of gap size)

In the present invention, the aforementioned void size can be quantified by the BET test method. Specifically, after 0.1 g of a sample (polysilicon porous body of the present invention) was put into a capillary of a specific surface area measuring device (manufactured by Micromeritics Co.: trade name ASAP2020), it was dried under reduced pressure at room temperature for 24 hours, and the voids The gas in the structure is degassed. Then, nitrogen gas was adsorbed on the aforementioned sample, and an adsorption isotherm was drawn to calculate the pore distribution. This allows the gap size to be evaluated.

The polysilicon porous body of the present invention exhibits a scratch resistance of 60 to 100% using Bemcot (registered trademark), for example, showing the strength of the film. The present invention is because it has such a film strength, so it has excellent scratch resistance in various processes. The present invention has scratch resistance in the production process, for example, when winding up and disposing the product film after producing the aforementioned polysilicon porous body. On the other hand, the polysilicon porous body of the present invention can use, for example, a catalyst reaction in a heating step described later as an alternative to reducing the porosity to increase the particle size of the crushed product of the gel-like silicon compound and the crushed products The bonding force of the necks bonded to each other by silicone. In this way, the polysilicon porous body of the present invention can impart a certain degree of strength to, for example, a fragile void structure.

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

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

(Assessment of scratch resistance)

(1) Sampling the void layer (polysiloxy porous body of the present invention) coated on the acrylic film to sample a round object with a diameter of about 15 mm.

(2) Next, silicon was identified with fluorescent X-rays (manufactured by Shimadzu Corporation: ZSX Primus II) for the aforementioned sample to measure the Si coating amount (Si ₀ ). Next, with respect to the void layer on the acrylic film, the void layer was cut into 50 mm × 100 mm from the periphery of the sample and fixed to a glass plate (thickness 3 mm), and then a sliding test was performed with Bemcot (registered trademark) . The sliding conditions were set to 100g weight, 10 reciprocating.

(3) Sampling and fluorescent X measurement are performed in the same manner as in the above (1) from the void layer where the sliding has ended, to detect the remaining amount of Si (Si ₁ ) after the scratch test. The scratch resistance is defined as the Si residual rate (%) 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(%)

For example, the polysilicon porous body of the present invention exhibits flexibility, and the number of times of folding endurance obtained by the MIT test is 100 or more. Since the present invention has such flexibility, for example, it is excellent in handleability during coiling or use during the manufacturing process.

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

The aforementioned flexibility means, for example, the easy deformability of a substance. The number of times of folding endurance obtained by the aforementioned MIT test can be measured by the following method, for example.

(Evaluation of folding endurance test)

After cutting the aforementioned void layer (polysilicon porous body of the present invention) into a short strip of 20 mm×80 mm, it was mounted on an MIT folding tester (manufactured by TESTER SANGYO CO,. LTD.: BE-202), Apply a load of 1.0N. R2.0mm is used as the chuck portion that encloses the void layer, and the number of times of folding endurance is at most 10,000 times, and the number of times when the void layer breaks is taken as the number of endurance of folding.

In the polysilicon porous body of the present invention, the film density is not particularly limited, and its lower limit is, for example, 1 g/cm ³ or more, 10 g/cm ³ or more, 15 g/cm ³ or more, and its upper limit is, for example, 50 g/cm ³ or less, 40 g /cm ³ or less, 30g/cm ³ or less, 2.1g/cm ³ or less, the range is for example 5~50g/cm ³ , 10~40g/cm ³ , 15~30g/cm ³ , 1~2.1g/cm ³ .

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

(Assessment of film density)

After the void layer (polysilicon porous body of the present invention) was formed on the acrylic film, the X-ray reflectivity of the total reflection area was measured using an X-ray diffraction device (manufactured by RIGAKU: RINT-2000). After blending Intensity and 2θ, calculate the porosity (P%) from the critical angle of total reflection of the void layer and substrate. The film density can be expressed by the following formula.

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

The polysiloxane porous body of the present invention may have a pore structure (porous structure) as described above, and may be, for example, an open foam structure having the pore structure continuously formed. The open foam structure, for example, means that the pore structure of the polysilicon porous body is connected in a three-dimensional pattern, and it can also be said that the internal voids of the pore structure are connected together. When the porous body has an open foam structure, the porosity of the bulk can be increased, but when using closed foam particles such as hollow silica, open foam cannot be formed structure. In contrast, the polysilica porous body of the present invention has a three-dimensional dendritic structure because of silica dioxide sol particles (a pulverized product of a gel-like silicon compound that forms a sol), so the coating film (containing the gel-like silicon The coating film of the sol of the pulverized compound of the compound) can easily form an open foam structure by sedimentation and accumulation of the aforementioned dendritic particles. In addition, the invention The polysilicon porous body is ideal to form an open foam structure with a monolith structure with a plurality of pores distributed. The above-mentioned monolithic structure refers to, for example, a structure having fine voids of nanometer size and a hierarchical structure in which an open foam structure having the same nanovoids is assembled. When the aforementioned monolithic structure is formed, for example, fine pores can be used to provide strength, and at the same time, coarse open foamed pores can be used to impart a high void ratio, thereby achieving both film strength and high void ratio. In order to form such a monolithic structure, for example, it is very important to control the pore distribution of the void structure to be generated in the gel-like silicon compound in the previous stage of pulverization into the pulverized product. In addition, for example, when pulverizing the gel-like silicon compound, the monolithic structure can be formed by controlling the particle size distribution of the pulverized material to a desired size.

In the polysilicon porous body of the present invention, the elongation rate at which tear marks showing flexibility are not particularly limited, and the lower limit is, for example, 0.1% or more, 0.5% or more, 1% or more, and the upper limit is, for example, 3% or less. The range of the elongation rate at which the tear marks are generated is, for example, 0.1 to 3%, 0.5 to 3%, and 1 to 3%.

The elongation rate at which the tear marks are generated can be measured by the following method, for example.

(Evaluation of elongation of tear marks)

After forming a void layer (polysilicon porous body of the present invention) on the acrylic film, a short strip sample of 5 mm×140 mm was taken out. Next, after the sample was clamped to a tensile testing machine (manufactured by Shimadzu Corporation: AG-Xplus) so that the distance between the clamps was 100 mm, a tensile test was performed 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 crack appeared in a part of the aforementioned sample, and the time at which the crack appeared Elongation (%) is the elongation generated by tear marks.

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

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

(Haze evaluation)

The void layer (polysilicon porous body of the present invention) was cut into a size of 50 mm×50 mm and mounted on a haze meter (Muragami Color Technology Research Institute Co., Ltd.: HM-150), and the haze was measured. The haze value can be calculated by the following formula.

Haze (%) = [diffused transmittance (%) / total light transmittance (%)] × 100 (%)

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

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

(Refractive index evaluation)

After forming a void layer (polysilicon porous body of the present invention) on the acrylic film, cut it into a size of 50 mm × 50 mm and attach it 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 (diameter about 20 mm) was painted black with a black marker to prepare a sample that does not reflect on the back surface of the glass plate. The aforementioned sample was mounted on an ellipsometer (manufactured by J.A. Woollam Japan: 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 was used as the refractive index.

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

The form of the polysilicon porous body of the present invention is not particularly limited, and may be, for example, a thin film or a bulk.

The manufacturing method of the polysilicon porous body of the present invention is not particularly limited, and for example, it can be manufactured by the manufacturing method of the polysilicon porous body mentioned in the introduction.

[4. Use of polysilicon porous body]

The polysilicone porous body manufactured using the coating material of the present invention can exert the same function as the air layer as described above, and therefore can be used for an object having the air layer instead of the air layer.

Examples of the member containing the porous silicone body include heat insulating materials, sound absorbing materials, dew condensation preventing materials, and optical members. These members can be used, for example, at locations where an air layer is required. The shape of these members is not particularly limited, and may be a thin film, for example.

In addition, examples of the member containing the porous polysilicon body include stent materials for regenerative medicine. As mentioned in the introduction, the aforementioned polysiloxane porous body has Porous structure with the same function as the air layer. The voids of the aforementioned polysilicon porous body are suitable for holding, for example, cells, nutrient sources, air, etc. Therefore, the aforementioned porous structure can be effectively used as a scaffold for regenerative medicine, for example.

The members containing the aforementioned polysilicon porous body may include, in addition to these, total reflection members, ink image receiving materials, single-layer AR (antireflection), single-layer moth eye, and dielectric constant materials Wait.

Examples

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

(Example 1)

In this example, the paint and the porous structure (polysilicon porous body) of the present invention were manufactured in the following manner.

(1) Gelation of silicon compounds

Dissolve 0.95g of silicon compound precursor MTMS in 2.2g of DMSO. 0.5 g of an aqueous solution of oxalic acid of 0.01 mol/L was added to the aforementioned mixed solution, and stirred at room temperature for 30 minutes to hydrolyze MTMS to produce ginseng (hydroxy)methylsilane.

After adding 0.38g of 28% ammonia water and 0.2g of pure water to 5.5g of DMSO, add the above-mentioned hydrolyzed mixture and stir for 15 minutes at room temperature to make ginseng (hydroxy)methylsilane gel To obtain a gel-like silicon compound.

(2) Ripening treatment

The above-mentioned gelatinized mixed solution was directly incubated at 40°C for 20 hours, and subjected to ripening treatment.

(3) Crushing treatment

Next, the aging-treated gel-like silicon compound is pulverized into particles having a size of several mm to several cm using a spatula. Here, 40 g of IPA was added, and after a little stirring, it was allowed to stand at room temperature for 6 hours, and the solvent and catalyst in the gel were decanted. After the same decantation treatment was repeated 3 times, the solvent substitution was ended. Then, the aforementioned gel-like silicon compound in the aforementioned mixed solution is subjected to high-pressure medium-less pulverization. This pulverization process uses a homogenizer (trade name UH-50, manufactured by SMT), weighs 1.18 g of gel and 1.14 g of IPA in a 5 cc screw bottle, and pulverizes under 50W and 20 kHz conditions for 2 minutes.

After the gelatinous silicon compound in the mixed solution is pulverized by the pulverization treatment, the mixed solution becomes the sol solution of the pulverized product. As a result of confirming the volume average particle size with a dynamic light-scattering Nanotrac particle size analyzer (manufactured by Nikkiso Co., Ltd., model UPA-EX150), the volume average particle size was 0.50 to 0.70. Particle size deviation. Furthermore, a 0.3% by weight KOH aqueous solution was prepared, and 0.02 g of catalyst KOH was added to 0.5 g of the aforementioned sol solution to prepare a coating liquid (catalyst-containing coating).

(4) Formation of coating film and formation of polysilicon porous body

Next, the coating liquid was applied on the surface of the base material made of polyethylene terephthalate (PET) by a bar coating method to form a coating film. The coating system is set to have 6 μL of the sol solution 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 cross-linking reaction of the pulverized product of the precursor. In this way, a 1 μm-thick polysilicon porous body formed by chemically combining the pulverized materials on the substrate is formed.

(Example 2)

Prepare an IPA (isopropanol) solution of 1.5% by weight of photobase generating catalyst (Wako Pure Chemical Industries, Ltd.: trade name WPBG266), and add KOH 0.031g of Example 1 to 0.75g of the aforementioned sol particle solution to prepare The coating liquid was subjected to UV irradiation of 350 mJ/cm ² (@360nm) after the formation of the coating film, except that the same operation as in Example 1 was performed to obtain a polysilicon porous body on the substrate. Furthermore, the porous body was heated and aged at 60°C for 20 hr to further increase the film strength.

(Example 3)

To the coating solution described in Example 2 was further added 0.018 g of 5% (by weight) bis(trimethoxysilyl)ethane to 0.75 g of the aforementioned sol solution, and the procedure was the same as in Example 2 except that the polymer was obtained. Silica porous body.

(Comparative example 1)

A porous body was formed in the same manner as in Example 1, except that the cultivation in the aging step was changed to 40° C. and a long-term aging of 72 hours.

(Comparative example 2)

Using TEOS (tetramethoxysilane) as a precursor of the silicon compound, and cultivating the aging step and changing the culturing step to 40°C and a long time of 72 hours, the same method as in Example 1 was used. A porous body is formed. In addition, in this comparative example, when the porous body (membrane) was made to be 1 μm thick, the film was partially broken, so the thickness was changed to 200 nm to form a film.

For Example 1, Comparative Example 1 and Comparative Example 2, the refractive index, the ratio of residual silanol groups and the scratch resistance were measured. These results are shown in Table 1 below.

As shown in Table 1 above, the polysilicon porous body (void layer) formed using the sol solution prepared in Example 1 was confirmed to have a thickness of 1 μm, a refractive index of less than 1.2, and film strength was also easily obtained. In addition, although not shown in Table 1, in Examples 2 and 3, it was confirmed that the refractive index was low and the film strength was high. On the other hand, when the sol solution of Comparative Example 1 is used, since the aging is carried out for a long time, there is almost no silanol group remaining in the gel. Therefore, a cross-linked structure is not formed in the bonding step, and sufficient film strength cannot be obtained. In addition, the sol solution of Comparative Example 2 uses TEOS as a precursor of the silicon compound. Therefore, although a high film strength is obtained, the flexibility is also significantly reduced. Therefore, in order to balance the strength and flexibility of the film, it is extremely useful to adjust the precursor of the silicon compound and the residual silanol group.

(Example 4)

In this example, the paint and the porous structure (polysilicon porous body) of the present invention were manufactured in the following manner.

First, in the same manner as in Example 1, the aforementioned "(1) Gelation of silicon compound" and "(2) Aging treatment" were performed. Next, the 0.3% by weight KOH aqueous solution was replaced, and an IPA (isopropanol) solution of 1.5% by weight photobase generating catalyst (Wako Pure Chemical Industries, Ltd.: trade name WPBG266) was added to the sol particle liquid. , Except for the same as Example 1 The above-mentioned "(3) Crushing treatment" is used to prepare the coating liquid (catalyst-containing coating). The addition amount of the IPA solution of the photobase generating catalyst to 0.075 g of the sol particle liquid was 0.031 g. Thereafter, in the same manner as in Example 1, the aforementioned "(4) Formation of coating film and formation of polysilicon porous body" were performed. The dried porous body prepared in the above-mentioned manner is irradiated with UV. The aforementioned UV irradiation is light with a wavelength of 360 nm, and the light irradiation amount (energy) is set to 500 mJ. Furthermore, after UV irradiation, heating and aging were carried out at 60° C. for 22 hr to form the porous structure of this example.

(Example 5)

After heating and aging without UV irradiation, the same operation as in Example 4 was carried out to form a paint and a porous structure (polysilicon porous body).

(Example 6)

After adding the IPA solution of the photobase to produce the catalyst, 0.018g of 5 wt% bis(trimethoxy)silane was added to the above sol solution 0.75g to adjust the coating liquid, except that the same operation as in Example 4 was carried out. Formation of paint and porous structure (polysilicon porous body).

(Example 7)

The addition amount of the IPA solution for the photobase generating catalyst to 0.75 g of the aforementioned sol solution was 0.054 g. Except for this, the same operation as in Example 4 was performed to form a paint and a porous structure (polysilicon porous body).

(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 an adhesive (adhesive layer) on one side was attached to the foregoing at room temperature before heating and aging. After the porous body, at 60 Heating and aging at ℃ for 22hr. Except for this, the same operation as in Example 4 was carried out to form a paint and a porous structure (polysilicon porous body).

(Example 9)

After the PET film was attached, heating and aging were not carried out, and the same operations as in Example 8 were carried out to form a paint and a porous structure (polysilicon porous body).

(Example 10)

After the IPA solution of the photobase generating catalyst was added, 0.018 g of 5 wt% bis(trimethoxy)silane was further added to 0.75 g of the aforementioned sol solution to adjust the coating liquid, except that the same operation as in Example 8 was performed. And the formation of paint and porous structure (polysilicon porous body).

(Example 11)

The addition amount of the IPA solution for the photobase generating catalyst to 0.75 g of the sol solution was 0.054 g. Except for this, the same operation as in Example 8 was carried out to form a paint and a porous structure (polysilicon porous body).

For the porous structures of Examples 4 to 11, the refractive index, adhesive peel strength and haze were measured by the aforementioned method, 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 rolls were in a state of being bonded to the PET film and the adhesive layer, so the attachment of the PET film and the acrylic adhesive was omitted. In addition, the storage stability of the coating solutions (catalyst-containing coatings) of Examples 4 to 11 are also shown in Tables 2 and 3. This storage stability is the result of visually confirming whether the coating liquid has changed after being left at room temperature for 1 week.

As shown in Tables 2 and 3 above, in the prepared polysilicon porous bodies of Examples 4 to 11 with a thickness of 1 μm, the refractive indexes are all at extremely low values of 1.14 to 1.16. In addition, these ultra-low refractive index layers even have extremely low haze values of 0.4, so it is confirmed that the transparency is also extremely high. In addition, since the ultra-low refractive index layers of Examples 4 to 11 have high adhesive peel strength, it was confirmed that even when wound into a roll, they still have high strength that is not easily peeled from other layers of the laminated film roll. In addition, the polysiloxane porous bodies of Examples 4 to 11 were confirmed to have extremely high scratch resistance. In addition, the coating solutions (catalyst-containing coatings) of Examples 4 to 11 confirmed that there was no change after 1 week of storage by visual observation, which also confirmed that the storage stability was good, and stable quality polysilicon could be efficiently produced Oxygen porous body.

Industrial availability

As described above, the paint produced by the production method of the present invention contains the pulverized product of the gel-like silicon compound and the pulverized product contains residual silanol groups. Therefore, for example, a coating film is formed by using the coating material, and then the coating The above-mentioned pulverized materials of the film are chemically combined to produce a porous structure with voids. In this way, the porous structure formed by using the paint can perform the same function as the air layer mentioned in the introduction. In addition, as described above, the porous structure can be fixed by chemically bonding the pulverized products to each other. Therefore, although the porous structure obtained has a void structure, it can still maintain sufficient strength. Therefore, the aforementioned porous structure can easily and simply impart a silanol porous body 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 material for regenerative medicine, an anti-condensation material, an optical member, etc., instead of the air layer, for example. Therefore, the manufacturing method of the present invention and the coating prepared therefrom can, for example, effectively manufacture the porous structure as mentioned in the introduction.

Claims (17)

A polysilicone sol coating, characterized in that it contains a pulverized product of a gel-like silicon compound and a dispersion medium, and the gel-like silicon compound is made of a silicon compound containing at least a saturated bond functional group of less than 3 functions; The pulverized material contains 1 to 50 mol% of residual silanol groups; and the polysilicone sol coating is a coating for chemically combining the pulverized materials with each other. The coating according to claim 1, wherein the volume average particle size of the aforementioned pulverized product is 0.05 to 2.00 μm. The coating according to claim 1 or 2, wherein the aforementioned silicon 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 linear alkyl or branched, respectively Alkyl groups, R ¹ and R ² may be the same or different from each other. When X ^{1 is} R ¹ , R ¹ may be the same or different from each other, and R ² may be the same or different from each other;

The coating material according to claim 1 or 2, which contains a catalyst for chemically combining the aforementioned crushed materials with each other. The coating material according to claim 1 or 2, further contains a cross-linking auxiliary agent for indirectly combining the aforementioned pulverized products. The coating material according to claim 5, wherein the content rate of the cross-linking auxiliary agent is 0.01 to 20% by weight relative to the weight of the pulverized product. A coating raw material, characterized in that it is a raw material containing a gel-like silicon compound and used to manufacture a polysilicone sol paint according to any one of claims 1 to 6, the gel-like silicon compound is composed of at least 3 functions The following silicon compounds with saturated bond functional groups were prepared. A coating raw material, characterized in that it is a raw material containing a gel-like silicon compound and used to manufacture a polysilicone sol paint according to any one of claims 1 to 6, the gel-like silicon compound is composed of at least 3 functions The gels made of the following silicon compounds with saturated bond functional groups have been cooked. A method for manufacturing a polysilicone sol paint according to any one of claims 1 to 6, characterized in that it includes a mixing step of mixing the crushed material of the gel-like silicon compound with a dispersion medium, the gel-like silicon The compound is prepared from a silicon compound containing at least 3 functional groups with a saturated bond or less. The manufacturing method of claim 9, further comprising a step of adding a cross-linking auxiliary agent in the mixing step, the cross-linking auxiliary agent is used to indirectly combine the pulverized substances of the gel-like silicon compound. The manufacturing method according to claim 10, wherein the added amount of the cross-linking auxiliary agent is 0.01 to 20% by weight relative to the weight of the pulverized product of the gel-like silicon compound. The manufacturing method according to any one of claims 9 to 11, further comprising a pulverizing step of pulverizing the gel-like silicon compound in a solvent; and using the pulverized product obtained by the pulverizing step in the mixing step. The manufacturing method according to claim 12, further comprising a gelation step of gelling the silicon compound in a solvent to generate the gel-like silicon compound; and using the gelation step in the pulverization step The aforementioned gel-like silicon compound. The manufacturing method according to claim 13, further comprising a aging step of aging the gel-like silicon compound in a solvent, and using the gel-like silicon compound after the aging step in the gelation step. The production method according to claim 14, wherein in the aging step, the gel-like silicon compound is cultured in the solvent at a temperature of 30° C. or higher and matured. A method for manufacturing a coating material as claimed in claim 7, characterized by comprising a gelation step of gelling a silicon compound in a solvent to produce a gel-like silicon compound, the silicon compound containing at least a saturated bond of less than 3 functions Functional group. A method for manufacturing a coating material as claimed in claim 8, characterized in that it includes a maturation step of maturing the gel-like silicon compound in a solvent, the gel-like silicon compound is composed of a functional group containing at least 3 or less saturated bond functional groups Made of silicon compounds.

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