WO2017131220A1 - Procédé de production de liquide contenant un gel pulvérisé - Google Patents

Procédé de production de liquide contenant un gel pulvérisé Download PDF

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Publication number
WO2017131220A1
WO2017131220A1 PCT/JP2017/003076 JP2017003076W WO2017131220A1 WO 2017131220 A1 WO2017131220 A1 WO 2017131220A1 JP 2017003076 W JP2017003076 W JP 2017003076W WO 2017131220 A1 WO2017131220 A1 WO 2017131220A1
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Prior art keywords
gel
pulverization
solvent
concentration
pulverized product
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PCT/JP2017/003076
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English (en)
Japanese (ja)
Inventor
大輔 服部
成鎭 柳
細川　和人
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日東電工株式会社
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Publication of WO2017131220A1 publication Critical patent/WO2017131220A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques

Definitions

  • the present invention relates to a method for producing a gel pulverized product-containing liquid.
  • gel-containing product-containing liquids that can form a void structure using a porous material such as a silica compound material (silicon compound material) as a raw material.
  • a porous body such as a silica compound is once gelled (gelation step), and the gelled porous body (porous gel) is pulverized (pulverization step).
  • the void structure is formed by coating the manufactured gel pulverized product-containing liquid.
  • the void structure can be applied to various objects, for example, as a void layer, and specifically to an optical member or the like.
  • Patent Document 1 and Non-Patent Document 1 disclose that the porous gel is pulverized in one stage by ultrasonic treatment.
  • the gel produced by the gelation step is, for example, in a massive state. For this reason, for example, as in Patent Document 1, the pulverized gel is easily mixed with the solution in the mixing step by applying the pulverizing step. Thereby, it becomes easy to manufacture the gel-containing liquid.
  • the concentration is adjusted while performing multi-stage crushing, the gel and the solvent may not be mixed uniformly and may become non-uniform.
  • the concentration is adjusted in the coarse pulverization step prior to the final pulverization step, the gel-containing liquid is difficult to mix uniformly because the particle size of the gel pulverized product is large (coarse). For this reason, in order to make the gel and the solvent uniform, coarse pulverization must be performed again every time the concentration is adjusted. Further, it is difficult to adjust the concentration after the final pulverization (for example, nano-pulverization in which gel particles are pulverized to a nanometer order particle size).
  • the gel pulverized product-containing liquid after the final pulverization step often requires a high concentration.
  • the particles may be aggregated because the particle size of the gel pulverized product is small.
  • the concentration is higher than the final target concentration, the viscosity becomes too high, and pulverization is difficult due to the occurrence of clogging in the pulverization process equipment. There is a risk.
  • an object of the present invention is to provide a method for producing a gel pulverized product-containing liquid having extremely excellent uniformity.
  • the method for producing a gel pulverized product-containing liquid of the present invention comprises a gel production step for producing a gel, a solvent substitution step for substituting the solvent in the gel with another solvent, and the gel And a gel pulverization step for pulverizing in the other solvent, wherein the pulverized product-containing liquid is produced by dividing the pulverization step into a plurality of pulverization steps, and after the solvent replacement step, It includes a concentration adjustment step of adjusting the concentration of the liquid containing the gel before the start of the first pulverization stage, and the concentration adjustment of the liquid containing the gel is not performed after the start of the first pulverization stage.
  • the pulverization step is performed by dividing it into a plurality of pulverization stages, and the concentration of the liquid containing gel is adjusted after the start of the first pulverization stage. Do not do. For this reason, a gel pulverized product-containing liquid with extremely excellent uniformity can be produced even in mass production at an industrial level.
  • FIG. 1 is a process cross-sectional view schematically showing an example of a method for forming a functional porous body 20 on a substrate 10 using the gel pulverized product-containing liquid of the present invention.
  • FIG. 2 is a diagram schematically showing a part of a process for producing a functional porous body using the gel pulverized product-containing liquid of the present invention and an example of an apparatus used therefor.
  • FIG. 3 is a diagram schematically showing a part of a process for producing a functional porous body using the gel pulverized product-containing liquid of the present invention and another example of an apparatus used therefor.
  • FIG. 4 is a process cross-sectional view schematically showing another example of a method for forming a functional porous body on a substrate in the present invention.
  • FIG. 5 is a diagram schematically showing a part of a process for producing a functional porous body using the gel pulverized product-containing liquid of the present invention and still another example of an apparatus used therefor.
  • FIG. 6 is a diagram schematically showing a part of a process for producing a functional porous body using the gel pulverized product-containing liquid of the present invention and still another example of an apparatus used therefor.
  • FIG. 7 is a process cross-sectional view schematically showing still another example of a method for forming a functional porous body on a substrate in the present invention.
  • FIG. 8 is a diagram schematically showing a part of a process for producing a functional porous body using the gel pulverized product-containing liquid of the present invention and still another example of an apparatus used therefor.
  • FIG. 9 is a diagram schematically showing a part of a process for producing a functional porous body using the gel pulverized product-containing liquid of the present invention and still another example of an apparatus used therefor.
  • the method for producing the gel pulverized product-containing liquid of the present invention is performed by dividing the pulverization step for pulverizing the gel into a plurality of pulverization steps.
  • the number of pulverization stages is not particularly limited, and may be two stages or three or more stages, for example.
  • the plurality of pulverization steps include a first pulverization step and a second pulverization step for pulverizing the gel
  • the first pulverization step includes: , Pulverizing the gel to obtain particles having a volume average particle diameter of 0.5 to 100 ⁇ m, and the second pulverizing step further pulverizes the particles after the first pulverization step to obtain volume average particles. It may be a stage where particles having a diameter of 10 to 1000 nm are formed.
  • the plurality of pulverization stages may or may not include a pulverization stage other than the first pulverization stage and the second pulverization stage.
  • the shape of the “particles” is not particularly limited, and may be, for example, spherical or non-spherical.
  • the particles of the pulverized product may be, for example, sol-gel bead-like particles, nanoparticles (hollow nanosilica / nanoballoon particles), nanofibers, or the like.
  • the gel is preferably a porous gel, and the pulverized product of the gel is preferably porous, but is not limited thereto.
  • the gel pulverized product may have, for example, a structure having at least one of a particle shape, a fiber shape, and a plate shape.
  • the particulate and flat structural units may be made of an inorganic substance, for example.
  • the constituent element of the particulate structural unit may include at least one element selected from the group consisting of Si, Mg, Al, Ti, Zn, and Zr, for example.
  • the structure (structural unit) that forms the particles may be a real particle or a hollow particle, and specifically includes silicone particles, silicone particles having fine pores, silica hollow nanoparticles, silica hollow nanoballoons, and the like.
  • the fibrous structural unit is, for example, a nanofiber having a diameter of nanometer, and specifically includes cellulose nanofiber, alumina nanofiber, and the like.
  • the plate-like structural unit include nanoclay, specifically, nano-sized bentonite (for example, Kunipia F [trade name]) and the like.
  • the fibrous structural unit is not particularly limited, but for example, from the group consisting of carbon nanofiber, cellulose nanofiber, alumina nanofiber, chitin nanofiber, chitosan nanofiber, polymer nanofiber, glass nanofiber, and silica nanofiber. It may be at least one fibrous material selected.
  • the plurality of pulverization steps (for example, the first pulverization step and the second pulverization step) are performed in the “other solvent” as described above.
  • the “other solvent” The details of the “other solvent” will be described later.
  • the “solvent” for example, the solvent for gel production, the solvent for void structure film production, the solvent for substitution, etc.
  • the “solvent” may not dissolve the gel or the pulverized product thereof.
  • the pulverized product or the like may be dispersed or precipitated in the solvent.
  • the volume average particle diameter of the gel after the first pulverization step may be, for example, 0.5 to 100 ⁇ m, 1 to 100 ⁇ m, 1 to 50 ⁇ m, 2 to 20 ⁇ m, or 3 to 10 ⁇ m.
  • the volume average particle diameter of the gel after the second pulverization step may be, for example, 10 to 1000 nm, 100 to 500 nm, or 200 to 300 nm.
  • the volume average particle diameter indicates the particle size variation of the pulverized product in the liquid containing the gel (gel-containing liquid).
  • the volume average particle diameter is measured by, for example, a particle size distribution evaluation apparatus such as a dynamic light scattering method and a laser diffraction method, and an electron microscope such as a scanning electron microscope (SEM) and a transmission electron microscope (TEM). Can do.
  • a particle size distribution evaluation apparatus such as a dynamic light scattering method and a laser diffraction method
  • an electron microscope such as a scanning electron microscope (SEM) and a transmission electron microscope (TEM).
  • the shear viscosity of the liquid immediately after the first pulverization step is, for example, 50 mPa / s or more, 1000 mPa ⁇ s or more, 2000 mPa ⁇ s or more, or 3000 mPa ⁇ s or more at a shear rate of 10001 / s.
  • it may be 100 Pa ⁇ s or less, 50 Pa ⁇ s or less, or 10 Pa ⁇ s or less.
  • the shear viscosity of the liquid immediately after the second pulverization step may be, for example, 1 mPa ⁇ s or more, 2 mPa ⁇ s or more, or 3 mPa ⁇ s or more, for example, 1000 mPa ⁇ s or less, 100 mPa ⁇ s or less, or It may be 50 mPa ⁇ s or less.
  • the method for measuring the shear viscosity is not particularly limited. For example, as described in the examples below, the shear viscosity can be measured using a vibration type viscosity measuring machine (trade name FEM-1000V, manufactured by Seconic).
  • the liquid containing the particles may have a shear viscosity of 50 mPa ⁇ s or more, and the particles may have a volume average particle diameter of 0.5 to 50 ⁇ m.
  • the gel concentration of the liquid containing the gel is, for example, 1% by weight or more, 1.5% by weight or more, 1.8% by weight or more, 2 It may be adjusted to 0.0 wt% or more, or 2.8 wt% or more, for example, 5 wt% or less, 4.5 wt% or less, 4.0 wt% or less, 3.8 wt% or less, or 3 It may be adjusted to 4% by weight or less.
  • the gel concentration of the liquid containing the gel is, for example, 1 to 5% by weight, 1.5 to 4.0% by weight, 2.0 to 3.8% by weight, or 2.8 to 3%.
  • the gel concentration is not too high so that the viscosity does not become too high. Further, from the viewpoint of use as a coating liquid described later, it is preferable that the gel concentration is not too low so that the viscosity does not become too low.
  • the gel concentration of the liquid containing the gel is measured, for example, by measuring the weight of the liquid and the weight of the solid content (gel) after removing the solvent of the liquid, and dividing the measured value of the latter by the former measured value. Can be calculated.
  • the concentration adjusting step for example, in order to appropriately adjust the gel concentration of the liquid containing the gel, the concentration may be decreased by adding a solvent, or the concentration may be increased by solvent volatilization.
  • the concentration adjustment step for example, if the gel concentration of the liquid containing the gel is measured, if the gel concentration is appropriate, the concentration is not decreased or the concentration is not increased (concentration adjustment). Alternatively, it may be used for the next step as it is.
  • the concentration adjusting step for example, if it is clear that the gel concentration of the liquid containing the gel is appropriate without measurement, the liquid containing the gel is not subjected to any measurement and concentration adjustment. You may use for the next process as it is.
  • the change in the weight% concentration of the liquid containing the gel from immediately before the start of the first pulverization step to immediately after the end of the final pulverization step is, for example, within ⁇ 3%, within ⁇ 2.8%, ⁇ 2 It may be within 6%, within ⁇ 2.4%, or within ⁇ 2.2%.
  • a gel form control step for controlling the shape and size of the gel is further included prior to the solvent replacement step.
  • the gel form control step it is preferable to control so that the size of the gel does not become too small. If the size of the gel is not too small, a large amount of solvent will adhere around the finely crushed gel, causing the measured value of the solvent concentration to be lower than the actual concentration or to remain higher than the actual concentration. This is because it is easy to prevent the problem that the measurement variation is large. Further, prior to the solvent replacement step, if the size of the gel is not too large, the solvent replacement efficiency is good.
  • each gel may become substantially uniform after the said gel form control process. If the size of each gel is almost uniform, dispersion of gel pulverized product-containing liquid between each lot of gel pulverized product particle size, gel concentration and other variations can be suppressed, and the gel pulverized product-containing solution has excellent uniformity. It is because it is easy to obtain.
  • the minor axis of the gel may be controlled to be, for example, 0.5 cm or more, 0.6 cm or more, 0.7 cm or more, or 0.8 cm or more, for example, 15 cm or less. , 13 cm or less, 10 cm or less, or 8 cm or less.
  • the major axis of the gel may be controlled to be, for example, 30 cm or less, less than 30 cm, 28 cm or less, 25 cm or less, or 20 cm or less, for example, 1 cm or more, 2 cm or more, You may control so that it may become 3 cm or more, 4 cm or more, or 5 cm or more.
  • the “minor axis” of a solid refers to a length measured at a position where the length is the shortest at a position where the length of the solid can be measured.
  • the “major axis” of a solid refers to a length measured at a place where the length is the longest at a place where the length of the solid can be measured.
  • the shape of the gel after the gel form control step is not particularly limited, and is, for example, a rectangular parallelepiped (including a cube), a cylindrical shape, a polygonal solid (for example, a polygonal column such as a triangular prism, a hexagonal column), a spherical shape, or What is necessary is just to control so that it may become an elliptical sphere (for example, shape like a rugby ball).
  • the shape of the gel is controlled to be a rectangular parallelepiped or a substantially rectangular parallelepiped.
  • the short side is controlled to be, for example, 0.5 cm or more, 0.6 cm or more, 0.7 cm or more, or 0.8 cm or more. For example, it may be controlled to be 15 cm or less, 13 cm or less, 10 cm or less, or 8 cm or less.
  • the said gel form control process when controlling so that the said gel may become a rectangular parallelepiped, even if it controls so that a long side may be 30 cm or less, less than 30 cm, 28 cm or less, 25 cm or less, or 20 cm or less, for example.
  • the “short side” of the rectangular parallelepiped refers to the shortest piece, and the “long side” refers to the longest piece.
  • the gel form control step may be performed, for example, after the gel manufacturing step, or may be performed during the gel manufacturing step (simultaneously with the gel manufacturing step). More specifically, for example, as follows.
  • the gel may be controlled to the solid by cutting the gel in a state where the gel is fixed.
  • the gel is extremely brittle, when the gel is cut, the gel may collapse unevenly regardless of the cutting direction. Therefore, by fixing the periphery of the gel, the pressure in the compression direction at the time of cutting is uniformly applied to the gel itself, so that the gel can be cut uniformly in the cutting direction.
  • the shape of the gel before the solvent replacement step is substantially a rectangular parallelepiped, and in the gel shape control step, five of the six surfaces of the substantially rectangular parallelepiped gel surface are in contact with other substances.
  • the gel may be cut by inserting a cutting jig into the gel from the exposed surface while the gel is fixed and the other surface is exposed.
  • the cutting jig is not particularly limited, and examples thereof include a knife, a wire-like thin jig, and a thin and sharp plate-like jig. Moreover, you may perform the cutting
  • the gel may be controlled to the solid by solidifying the gel raw material in a form (container) corresponding to the shape and size of the solid.
  • a form corresponding to the shape and size of the solid.
  • the gel concentration of the liquid containing the gel is measured, and the gel Only the liquid having a concentration within a predetermined numerical range may be subjected to the subsequent pulverization step.
  • the gel concentration it is necessary to be a uniform liquid.
  • the liquid is hard to separate to some extent with high viscosity after the pulverization step.
  • the gel concentration is not too high because the viscosity does not become too high, and from the viewpoint of using as a coating liquid, the viscosity is not too low. It is preferred that the gel concentration is not too low. For example, from such a point of view, only the liquid having the gel concentration within a predetermined numerical range may be consistently provided until after the final pulverization stage.
  • the predetermined numerical range of the gel concentration is, for example, as described above, and may be, for example, 2.8% by weight or more and 3.4% by weight or less, but is not limited thereto.
  • the gel concentration measurement may be performed after the end of the first pulverization stage and before the end of the final pulverization stage, but in addition to or instead of this, the solvent substitution step It may be performed either before or after the gel pulverization step and after the final pulverization step (for example, the second pulverization step).
  • concentration measurement for example, only the said liquid whose said gel density
  • the concentration control after the solvent replacement step and before the gel grinding step the amount of solvent adhering to the gel is unstable, and thus there may be a large variation in each measurement of the concentration measurement value. Therefore, it is preferable to control the shape and size of the gel to be substantially uniform by the above-described gel form control step prior to the concentration management after the solvent replacement step and before the gel grinding step. Thereby, the concentration can be stably measured. Thereby, for example, it is possible to manage the gel concentration of the gel-containing liquid in a unified and accurate manner.
  • At least one of the plurality of pulverization stages has a pulverization method different from at least one other pulverization stage.
  • the pulverization methods in the plurality of pulverization steps may all be different, but there may be a pulverization step performed by the same pulverization method.
  • all three stages may be performed in different ways (that is, using three pulverization methods), and any two pulverization steps may be performed in the same pulverization method. It is also possible to carry out the other pulverization step in a different pulverization mode.
  • the pulverization method is not particularly limited, and examples thereof include a cavitation method and a medialess method described later.
  • the gel pulverized product-containing liquid is, for example, a sol liquid containing particles (pulverized product particles) obtained by pulverizing the gel.
  • the plurality of pulverization steps include a coarse pulverization step and a main pulverization step, and after obtaining coarse sol particles by the coarse pulverization step, A sol particle maintaining a porous gel network may be obtained.
  • classification of the gel particles is performed.
  • the method further includes a step.
  • the production method of the present invention includes, for example, a gelation step in which a massive porous body is gelled in a solvent to form the gel.
  • a gelation step in which a massive porous body is gelled in a solvent to form the gel.
  • the gel gelled by the gelation process is used in the first pulverization stage (for example, the first pulverization stage) among the plurality of pulverization stages.
  • the production method of the present invention includes, for example, an aging step of aging the gelled gel in a solvent.
  • the gel after the aging step is used in the first pulverization step (for example, the first pulverization step) among the plurality of pulverization steps.
  • the solvent replacement step of replacing the solvent with another solvent is performed.
  • the gel in the other solvent is used in the first pulverization step (for example, the first pulverization step) among the plurality of pulverization steps.
  • At least one of the pulverization stages of the production method of the present invention for example, at least one of the first pulverization stage and the second pulverization stage, for example, while measuring the shear viscosity of the liquid, Control crushing of the porous body.
  • At least one of the plurality of pulverization steps is performed by, for example, high-pressure medialess pulverization.
  • the gel is, for example, a silicon compound gel containing at least a trifunctional or lower saturated bond functional group.
  • the gel crushed product-containing liquid obtained by the method for producing the gel crushed product-containing liquid of the present invention may be referred to as “the gel crushed product-containing liquid of the present invention”.
  • a functional porous body can be formed by forming a coating film and chemically bonding the pulverized products in the coating film.
  • the functional porous body can be applied to various objects.
  • the functional porous body obtained by using the gel pulverized product-containing liquid of the present invention for example, instead of an air layer, a heat insulating material, a sound absorbing material, a scaffold material for regenerative medicine, a dew condensation preventing agent, an optical member Can be used as etc. Therefore, the gel pulverized product-containing liquid and the method for producing the same according to the present invention are useful, for example, in the production of the functional porous body.
  • the gel pulverized product-containing liquid of the present invention has extremely excellent uniformity as described above, for example, when the functional porous body is applied to uses such as an optical member, the appearance is improved. can do.
  • the gel pulverized product-containing liquid of the present invention is, for example, for obtaining a layer having a high porosity (high porosity layer) by coating (coating) the gel pulverized product-containing liquid on a substrate and further drying.
  • a gel pulverized product-containing liquid may be used.
  • the gel pulverized product-containing liquid of the present invention may be, for example, a gel pulverized product-containing liquid for obtaining a high porosity porous material (large thickness or massive bulk material).
  • the bulk body can be obtained, for example, by performing bulk film formation using the gel pulverized product-containing liquid.
  • a step of producing the gel crushed product-containing liquid of the present invention by the method for producing a gel crushed product-containing liquid of the present invention, and a step of coating the gel crushed product-containing liquid on a substrate to form a coating film And the layer (high void layer) which has a high porosity can be manufactured with the manufacturing method including the process of drying the said coating film.
  • a production method may be referred to as “a method for producing a high void layer of the present invention”.
  • the high void layer produced by the method for producing a high void layer of the present invention may be referred to as “the high void layer of the present invention”.
  • the high void layer of the present invention may be, for example, a high void layer having a porosity of 60% by volume or more.
  • a high void can be obtained by a production method including the step of producing the gel crushed product-containing liquid of the invention by the method of producing the gel crushed product-containing liquid of the invention and the step of drying the gel crushed product-containing liquid.
  • a porous body having a high porosity (high porosity porous body) can be produced.
  • such a production method may be referred to as “a method for producing a high porosity porous material of the present invention”.
  • the high porosity porous material produced by the method for producing a high porosity porous material of the present invention may be referred to as “the high porosity porous material of the present invention”.
  • the high porosity porous body of the present invention may be, for example, a high porosity porous body having a porosity of 60% by volume or more.
  • the step of producing the gel crushed product-containing liquid of the present invention by the method for producing the gel crushed product-containing liquid of the present invention, the step of feeding out the roll-shaped resin film, and the above-mentioned resin film fed out A laminated film in which the high void layer is formed on the resin film after the step of coating the gel pulverized product-containing liquid to form a coating film, the step of drying the coating film, and the step of drying A laminated film roll can be produced by a production method including a step of winding up the film.
  • a production method may be referred to as a “production method of the laminated film roll of the present invention”.
  • the high porosity porous body manufactured by the manufacturing method of the laminated film roll of this invention may be called “the laminated film roll of this invention.”
  • the high void layer may be, for example, a high void layer having a porosity of 60% by volume or more.
  • the gel pulverized product-containing liquid of the present invention includes, for example, the gel pulverized product pulverized by the pulverization step (for example, the first pulverization step and the second pulverization step) and the other solvent.
  • the method for producing a gel pulverized product-containing liquid according to the present invention includes a plurality of pulverization steps for pulverizing the gel (for example, porous gel), and includes, for example, the first pulverization step and the first pulverization step. 2 grinding steps.
  • the case where the method for producing a gel pulverized product-containing liquid of the present invention includes the first pulverization step and the second pulverization step will be mainly described as an example.
  • the case where the said gel is a porous body (porous body gel) is mainly demonstrated.
  • the present invention is not limited to this, and the description of the case where the gel is a porous body (porous body gel) can be applied by analogy other than the case where the gel is a porous body.
  • the plurality of pulverization steps (for example, the first pulverization step and the second pulverization step) in the method for producing a gel pulverized product-containing liquid of the present invention may be collectively referred to as a “pulverization step”.
  • the gel pulverized product-containing liquid of the present invention can be used for the production of a functional porous body having the same function as the air layer (for example, low refractive index) as described later.
  • the gel pulverized product-containing liquid obtained by the production method of the present invention contains the pulverized product of the porous gel, and the pulverized product has a three-dimensional structure of the unpulverized porous gel destroyed. , A new three-dimensional structure different from the uncrushed porous gel can be formed. For this reason, for example, a coating film (precursor of a functional porous body) formed using the gel pulverized material-containing liquid is not obtained in a layer formed using the unground porous gel.
  • the gel pulverized product-containing liquid of the present invention has a new three-dimensional structure formed as the coating film (precursor of a functional porous body), for example, because the pulverized product contains residual silanol groups.
  • the pulverized product can be chemically bonded to each other.
  • the gel pulverized product-containing liquid obtained by the production method of the present invention is very useful, for example, in the production of the porous structure that can be used as a substitute for the air layer.
  • the air layer for example, it is necessary to form an air layer between the members by stacking the members with a gap provided therebetween via a spacer or the like.
  • the functional porous body formed using the gel pulverized product-containing liquid of the present invention can exhibit the same function as the air layer only by placing it at a target site. Therefore, as described above, functions similar to the air layer can be imparted to various objects more easily and simply than forming the air layer.
  • the porous structure can be used as, for example, a heat insulating material, a sound absorbing material, a regenerative medical scaffolding material, a dew condensation preventing material, etc., instead of an air layer.
  • the gel pulverized product-containing liquid of the present invention can also be referred to as, for example, the functional porous body forming solution or the low refractive layer forming solution.
  • the porous body is a pulverized product thereof.
  • the range of the volume average particle diameter of the pulverized product (porous gel particles) is, for example, 10 to 1000 nm, 100 to 500 nm, and 200 to 300 nm.
  • the said volume average particle diameter shows the particle size variation of the said ground material in the gel ground material containing liquid of this invention.
  • the volume average particle diameter is, for example, a particle size distribution evaluation apparatus such as a dynamic light scattering method or a laser diffraction method, and an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Can be measured.
  • the gel concentration of the pulverized product is not particularly limited.
  • particles having a particle size of 10 to 1000 nm are 2.5 to 4.5% by weight, 2.7 to 2.7%. It is 4.0% by weight and 2.8 to 3.2% by weight.
  • the gel for example, porous gel
  • examples thereof include a silicon compound.
  • the silicon compound is not particularly limited, and examples thereof include a silicon compound containing at least a trifunctional or lower saturated bond functional group.
  • the above-mentioned “including a saturated bond functional group having 3 or less functional groups” means that the silicon compound has 3 or less functional groups, and these functional groups are saturatedly bonded to silicon (Si). Means.
  • the silicon compound is, for example, a compound represented by the following formula (2).
  • R 1 and R 2 are each a linear or branched alkyl group, R 1 and R 2 may be the same or different, R 1 s may be the same as or different from each other when X is 2. R 2 may be the same as or different from each other.
  • X and R 1 are, for example, the same as X and R 1 in the formula (1).
  • R 2 is, for example, can be exemplified for R 1 is incorporated in the formula (1) described later.
  • the silicon compound represented by the formula (2) include a compound represented by the following formula (2 ′) in which X is 3.
  • R 1 and R 2 are the same as those in the formula (2), respectively.
  • the silicon compound is trimethoxy (methyl) silane (hereinafter also referred to as “MTMS”).
  • the concentration of the pulverized product of the porous gel in the solvent is not particularly limited, and is, for example, 0.3 to 50% (v / v), 0.5 to 30% ( v / v), 1.0 to 10% (v / v).
  • concentration of the pulverized product is too high, for example, the fluidity of the gel pulverized product-containing liquid is remarkably lowered, and there is a possibility of generating aggregates and coating streaks during coating.
  • the concentration of the pulverized product is too low, for example, not only does it take a considerable time to dry the solvent, but also the residual solvent immediately after drying increases, so the porosity may decrease. .
  • the physical properties of the gel pulverized product-containing liquid of the present invention are not particularly limited.
  • the shear viscosity of the gel pulverized product-containing liquid is, for example, 1 mPa ⁇ s to 1 Pa ⁇ s, 1 mPa ⁇ s to 500 mPa ⁇ s, 1 mPa ⁇ s to 50 mPa ⁇ s, 1 mPa ⁇ s at a shear rate of 10001 / s.
  • shear viscosity is too high, for example, coating streaks may occur, and defects such as a decrease in the transfer rate of gravure coating may be observed.
  • shear viscosity is too low, for example, the wet coating thickness at the time of coating cannot be increased, and a desired thickness may not be obtained after drying.
  • examples of the solvent include a dispersion medium.
  • the dispersion medium (hereinafter also referred to as “coating solvent”) is not particularly limited, and examples thereof include a gelling solvent and a grinding solvent described later, and the grinding solvent is preferable.
  • the coating solvent includes an organic solvent having a boiling point of 70 ° C. or higher and lower than 180 ° C. and a saturated vapor pressure at 20 ° C. of 15 kPa or lower.
  • organic solvent examples include carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene, isobutyl alcohol, isopropyl alcohol, isopentyl alcohol, 1-pentyl alcohol (pentanol), Ethyl alcohol (ethanol), ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-normal-butyl ether, ethylene glycol monomethyl ether, xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isopentyl acetate, ethyl acetate, Normal-butyl acetate, normal-propyl acetate, normal-pentyl acetate, cyclohexanol, cyclohexanone, 1,4-dioxane N, N-dimethylformamide, st
  • the gel pulverized material-containing liquid of the present invention includes, for example, a sol particle liquid that is the sol-like pulverized material dispersed in the dispersion medium.
  • the gel pulverized product-containing liquid of the present invention for example, continuously forms a void layer having a film strength of a certain level or more by performing chemical crosslinking by a bonding step described later after coating and drying on a substrate.
  • “sol” means that a three-dimensional structure of a gel is pulverized so that a pulverized product (that is, a nano-three-dimensional porous sol particle retaining a part of a void structure) is dissolved in a solvent. The state which disperse
  • the gel pulverized product-containing liquid of the present invention may contain, for example, a catalyst for chemically bonding the gel pulverized products.
  • the content of the catalyst is not particularly limited, and is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight with respect to the weight of the pulverized product of the gel. .
  • the gel pulverized product-containing liquid of the present invention may further contain, for example, a crosslinking aid for indirectly bonding the gel pulverized products.
  • a crosslinking aid for indirectly bonding the gel pulverized products.
  • the content of the crosslinking aid is not particularly limited.
  • the content 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 gel. It is.
  • the proportion of functional groups that do not contribute to the intra-gel cross-linking structure among the functional groups of the constituent monomer of the gel is, for example, 30 mol% or less, 25 mol% or less, 20 mol. % Or less, 15 mol% or less, for example, 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more may be sufficient.
  • the ratio of the functional group that does not contribute to the in-gel crosslinked structure can be measured, for example, as follows.
  • the mixing step is a step of mixing the porous gel particles (pulverized product) and the solvent, and may or may not be present.
  • the mixing step for example, there is a step of mixing a pulverized product of a gel-like silicon compound (silicon compound gel) obtained from a silicon compound containing at least a trifunctional or lower saturated bond functional group and a dispersion medium.
  • the pulverized product of the porous gel can be obtained from the porous gel by a pulverization step described later.
  • the pulverized product of the porous gel can be obtained, for example, from the porous gel after the aging treatment in which the aging step described later is performed.
  • the gelation step is, for example, a step of gelling a massive porous body in a solvent to form the porous body gel.
  • the at least 3 This is a step of producing a silicon compound gel by gelling a silicon compound containing a functionally saturated functional bond group in a solvent.
  • the gelation step will be described by taking the case where the porous body is a silicon compound as an example.
  • the gelation step is, for example, a step of gelling the monomer silicon compound by a dehydration condensation reaction in the presence of a dehydration condensation catalyst, whereby a silicon compound gel is obtained.
  • the silicon compound gel has, for example, residual silanol groups, and the residual silanol groups are preferably adjusted as appropriate according to chemical bonding between the pulverized products of the silicon compound gel described later.
  • the silicon compound is not particularly limited as long as it is gelled by a dehydration condensation reaction.
  • the silicon compounds are bonded.
  • the bond between the silicon compounds is, for example, a hydrogen bond or an intermolecular force bond.
  • Examples of the silicon compound include a silicon compound represented by the following formula (1). Since the silicon compound of the formula (1) has a hydroxyl group, the silicon compound of the formula (1) can be hydrogen bonded or intermolecularly bonded through, for example, each hydroxyl group.
  • X is 2, 3 or 4
  • R 1 is a linear or branched alkyl group.
  • the carbon number of R 1 is, for example, 1-6, 1-4, 1-2.
  • Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • Examples of the branched alkyl group include an isopropyl group and an isobutyl group.
  • X is, for example, 3 or 4.
  • the silicon compound represented by the formula (1) include a compound represented by the following formula (1 ′) in which X is 3.
  • R 1 is the same as in the above formula (1), and is, for example, a methyl group.
  • the silicon compound is tris (hydroxy) methylsilane.
  • X is 3, the silicon compound is, for example, a trifunctional silane having three functional groups.
  • silicon compound represented by the formula (1) examples include a compound in which X is 4.
  • the silicon compound is, for example, a tetrafunctional silane having four functional groups.
  • the silicon compound may be, for example, a precursor that forms the silicon compound of the formula (1) by hydrolysis.
  • the precursor is not particularly limited as long as it can generate the silicon compound by hydrolysis, and specific examples thereof include a compound represented by the formula (2).
  • the production method of the present invention may include, for example, a step of hydrolyzing the precursor prior to the gelation step.
  • the hydrolysis method is not particularly limited, and can be performed, for example, by a chemical reaction in the presence of a catalyst.
  • the catalyst include acids such as oxalic acid and acetic acid.
  • the hydrolysis reaction can be performed, for example, by slowly dropping an aqueous solution of oxalic acid into the dimethyl sulfoxide solution of the silicon compound precursor in a room temperature environment and then stirring the mixture for about 30 minutes.
  • hydrolyzing the silicon compound precursor for example, by completely hydrolyzing the alkoxy group of the silicon compound precursor, further heating and immobilization after gelation / aging / void structure formation, It can be expressed efficiently.
  • examples of the silicon compound include a hydrolyzate of trimethoxy (methyl) silane.
  • the silicon compound of the monomer is not particularly limited, and can be appropriately selected according to the use of the functional porous body to be produced, for example.
  • the silicon compound is preferably the trifunctional silane from the viewpoint of excellent low refractive index property, and also has strength (for example, scratch resistance).
  • the tetrafunctional silane is preferable from the viewpoint of excellent scratch resistance.
  • the said silicon compound used as the raw material of the said silicon compound gel may use only 1 type, for example, and may use 2 or more types together.
  • the silicon compound may include, for example, only the trifunctional silane, may include only the tetrafunctional silane, may include both the trifunctional silane and the tetrafunctional silane, Furthermore, other silicon compounds may be included.
  • the ratio is not particularly limited and can be set as appropriate.
  • the gelation of the porous body such as the silicon compound can be performed, for example, by a dehydration condensation reaction between the porous bodies.
  • the dehydration condensation reaction is preferably performed, for example, in the presence of a catalyst.
  • the catalyst include acid catalysts such as hydrochloric acid, oxalic acid, and sulfuric acid, and ammonia, potassium hydroxide, sodium hydroxide, ammonium hydroxide, and the like.
  • a dehydration condensation catalyst such as a base catalyst.
  • the dehydration condensation catalyst may be an acid catalyst or a base catalyst, but a base catalyst is preferred.
  • the amount of the catalyst added to the porous body is not particularly limited, and for example, 0.01 to 10 mol, 0.05 to 7 mol, 0.1 to 5 moles.
  • the gelation of the porous body such as the silicon compound is preferably performed in a solvent, for example.
  • the ratio of the porous body in the solvent is not particularly limited.
  • the solvent include dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc), dimethylformamide (DMF), ⁇ -butyllactone (GBL), acetonitrile (MeCN), ethylene Examples thereof include glycol ethyl ether (EGEE).
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • DMAc N, N-dimethylacetamide
  • DMF dimethylformamide
  • GBL ⁇ -butyllactone
  • MeCN acetonitrile
  • ethylene examples thereof include glycol ethyl ether (EGEE).
  • one type of solvent may be used, or two or more types may be used in combination.
  • the solvent used for the gelation is
  • the gelation conditions are not particularly limited.
  • the treatment temperature for the solvent containing the porous body is, for example, 20 to 30 ° C., 22 to 28 ° C., 24 to 26 ° C., and the treatment time is, for example, 1 to 60 minutes, 5 to 40 minutes, 10 to 30 Minutes.
  • the process conditions in particular are not restrict
  • the gel form of the porous body obtained in the gelation step is not particularly limited.
  • “Gel” generally refers to a solidified state in which a solute has a structure in which it loses independent motility due to interaction and aggregates.
  • a wet gel includes a dispersion medium and a solute has a uniform structure in the dispersion medium.
  • a xerogel is a network structure in which the solvent is removed and the solute has voids.
  • the silicon compound gel is preferably a wet gel, for example.
  • the remaining silanol group of the silicon compound gel is not particularly limited, and examples thereof include the ranges described later.
  • the porous gel obtained by the gelation may be subjected, for example, to the solvent replacement step and the first pulverization step as it is, but prior to the first pulverization step, an aging treatment is performed in the aging step. You may give it.
  • the gelled porous body (porous gel) is aged in a solvent.
  • conditions for the aging treatment are not particularly limited, and for example, the porous gel may be incubated in a solvent at a predetermined temperature. According to the aging treatment, for example, the porous particles having a three-dimensional structure obtained by gelation can further grow the primary particles, thereby increasing the size of the particles themselves. is there.
  • the contact state of the neck portion where the particles are in contact can be increased from point contact to surface contact, for example.
  • the porous gel subjected to the aging treatment 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 pulverized product after pulverization can be further improved.
  • the pore size of the void structure in which the three-dimensional basic structure is deposited It can suppress shrinking
  • the lower limit of the temperature of the aging treatment is, for example, 30 ° C. or more, 35 ° C. or more, 40 ° C. or more, and the upper limit thereof is, for example, 80 ° C. or less, 75 ° C. or less, 70 ° C. or less.
  • the predetermined time is not particularly limited, and the lower limit thereof is, for example, 5 hours or more, 10 hours or more, 15 hours or more, and the upper limit thereof is, for example, 50 hours or less, 40 hours or less, 30 hours or less.
  • the range is, for example, 5 to 50 hours, 10 to 40 hours, 15 to 30 hours.
  • the optimum conditions for aging are preferably set, for example, as described above, so that an increase in the size of the primary particles and an increase in the contact area of the neck portion can be obtained in the porous gel.
  • the temperature of the aging treatment preferably takes into account, for example, the boiling point of the solvent used.
  • the aging treatment for example, if the aging temperature is too high, the solvent is excessively volatilized, and there is a possibility that problems such as closing of the pores of the three-dimensional void structure occur due to the concentration of the coating solution. is there.
  • the aging treatment for example, if the aging temperature is too low, the effect due to the aging is not sufficiently obtained, temperature variation with time of the mass production process increases, and a product with poor quality may be produced. There is.
  • the same solvent as in the gelation step can be used, and specifically, the reaction product after the gel treatment (that is, the solvent containing the porous gel) may be applied as it is. preferable.
  • the porous gel is the silicon compound gel
  • the number of moles of residual silanol groups contained in the silicon compound gel after the aging treatment after gelation is, for example, the raw material used for the gelation (for example, the above-mentioned Silicon compound or precursor thereof) is the ratio of residual silanol groups when the number of moles of alkoxy groups is 100, and the lower limit is, for example, 50% or more, 40% or more, 30% or more, and the upper limit is For example, it is 1% or less, 3% or less, 5% or less, and the range is, for example, 1 to 50%, 3 to 40%, or 5 to 30%.
  • the lower the number of moles of residual silanol groups For the purpose of increasing the hardness of the silicon compound gel, for example, the lower the number of moles of residual silanol groups, the better.
  • the number of residual silanol groups is too high, for example, in the formation of the functional porous body, there is a possibility that the void structure cannot be maintained before the functional porous body precursor is crosslinked.
  • the number of moles of residual silanol groups is too low, for example, in the bonding step, the precursor of the functional porous body cannot be crosslinked, and sufficient film strength may not be imparted.
  • the above is an example of residual silanol groups.
  • the silicon compound modified with various reactive functional groups as a raw material of the silicon compound gel, The same phenomenon can be applied.
  • the porous gel obtained by the gelation is subjected to, for example, a aging treatment in the aging step, a solvent replacement step, and then subjected to the pulverization step.
  • the solvent replacement step the solvent is replaced with another solvent.
  • the pulverizing step is a step of pulverizing the porous gel as described above.
  • the pulverization may be performed, for example, on the porous gel after the gelation step, or may be performed on the post-ripening porous gel that has been subjected to the aging treatment.
  • a gel form control step for controlling the shape and size of the gel may be performed prior to the solvent replacement step (for example, after the aging step).
  • the shape and size of the gel controlled in the gel form control step are not particularly limited, but are as described above, for example.
  • the gel form control step may be performed, for example, by dividing (for example, cutting) the gel into a solid (three-dimensional body) having an appropriate size and shape.
  • the gel is subjected to the solvent replacement step and then the pulverization step.
  • the solvent replacement step the solvent is replaced with another solvent. If the solvent is not replaced with the other solvent, for example, the catalyst and the solvent used in the gelation step remain after the aging step, and further gelation occurs over time, resulting in gel pulverization finally obtained This is because the pot life of the product-containing liquid may be affected, and the drying efficiency when the coating film formed using the gel pulverized product-containing liquid is dried may be decreased.
  • the other solvent in the gel pulverization step is also referred to as a “grinding solvent”.
  • the solvent for pulverization is not particularly limited, and for example, an organic solvent can be used.
  • the organic solvent include solvents having a boiling point of 140 ° C. or lower, 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, n-butanol, 2-butanol, isobutyl alcohol, pentyl alcohol, propylene glycol monomethyl ether (PGME), methyl cellosolve, acetone and the like.
  • the pulverizing solvent may be, for example, one type or a combination of two or more types.
  • the solvent replacement step is divided into a plurality of solvent replacement steps.
  • the step performed later is more than the step performed earlier.
  • the hydrophilicity of the other solvent may be lowered.
  • the solvent replacement efficiency can be improved, and the residual amount of the gel production solvent (for example, DMSO) in the gel can be made extremely low.
  • the solvent replacement step is divided into three solvent replacement steps. In the first solvent replacement step, DMSO in the gel is first replaced with water, and then the second solvent replacement step. Then, the water in the gel may be replaced with IPA, and the IPA in the gel may be replaced with isobutyl alcohol in the third replacement step.
  • the combination of the gelling solvent and the grinding solvent is not particularly limited.
  • a more uniform coating film can be formed in the coating film formation described below.
  • the solvent replacement step is not particularly limited, but can be performed as follows, for example. That is, first, the gel produced by the gel production process (for example, the gel after the aging treatment) is immersed or brought into contact with the other solvent, the gel production catalyst in the gel, and the alcohol component produced by the condensation reaction. , Water and the like are dissolved in the other solvent. Thereafter, the solvent in which the gel is immersed or contacted is discarded, and the gel is immersed or contacted again in a new solvent. This is repeated until the residual amount of the solvent for gel production in the gel reaches a desired amount.
  • the immersion time per time is, for example, 0.5 hours or more, 1 hour or more, or 1.5 hours or more, and the upper limit is not particularly limited, but for example, 10 hours or less.
  • the immersion of the solvent may be handled by continuous contact of the solvent with the gel.
  • the temperature during the immersion is not particularly limited, but may be, for example, 20 to 70 ° C, 25 to 65 ° C, or 30 to 60 ° C.
  • the solvent replacement proceeds quickly, and the amount of solvent necessary for the replacement may be small.
  • the solvent replacement may be simply performed at room temperature. For example, when the solvent replacement step is performed in a plurality of solvent replacement steps, each of the plurality of solvent replacement steps may be performed as described above.
  • a gel pulverization step is performed in which the gel is pulverized in the pulverization solvent.
  • the gel concentration may be measured as necessary, and then the gel concentration adjustment step may be performed as necessary. good.
  • the gel concentration measurement after the solvent replacement step and before the gel pulverization step can be performed, for example, as follows. That is, first, after the solvent replacement step, the gel is taken out from the other solvent (grinding solvent). For example, the gel is controlled to a lump having an appropriate shape and size (for example, a block shape) by the gel form control step.
  • the solid content concentration in one lump of gel is measured by a weight drying method.
  • the measurement is performed with a plurality of (for example, six) chunks taken at random, and the average value and the variation in value are calculated.
  • the gel concentration of the gel-containing liquid may be decreased by further adding the other solvent (grinding solvent).
  • concentration adjustment process may raise the gel density
  • the pulverization step is divided into a plurality of pulverization steps, specifically, for example, the first pulverization step and Performing the second grinding step.
  • the pulverization step may be further performed in addition to the first pulverization step and the second pulverization step. That is, in the production method of the present invention, the pulverization step is not limited to only two pulverization steps, and may include three or more pulverization steps.
  • the first pulverization step is a step of pulverizing the porous gel.
  • the second pulverization step is a step of further pulverizing the porous gel particles after the first pulverization step.
  • the volume average particle diameter of the porous gel particles obtained by the first pulverization step and the volume average particle diameter of the porous gel particles obtained by the second pulverization step are, for example, as described above. It is.
  • the method for measuring the volume average particle diameter is also as described above, for example.
  • the shear viscosity of the gel pulverized product-containing liquid immediately after the first pulverization stage and immediately after the second pulverization stage is, for example, as described above.
  • the method for measuring the shear viscosity is also as described above, for example.
  • the gel concentration of the gel-containing liquid is measured, and only the liquid having the gel concentration within a predetermined numerical range is used for the second pulverization step.
  • the concentration of the gel-containing liquid may be managed.
  • the method for pulverizing the porous gel is not particularly limited, and may be performed by, for example, a high-pressure medialess pulverizer, an ultrasonic homogenizer, a high-speed rotary homogenizer, a high-pressure extrusion pulverizer, or other wet medialess pulverizer using a cavitation phenomenon. Can do.
  • the first pulverization step and the second pulverization step may be performed by the same pulverization method or by different pulverization methods, but it is preferable to perform different pulverization methods.
  • the pulverization method it is preferable that at least one of the first pulverization step and the second pulverization step is performed by a method of pulverizing the porous gel by controlling energy.
  • the method of pulverizing the porous gel by controlling the energy include a method performed by a high-pressure medialess pulverizer.
  • the pulverization strength is strong, but pulverization control (adjustment) is difficult.
  • it is the method of grind
  • a uniform gel pulverized product-containing liquid can be produced with a limited amount of work. For this reason, the gel pulverized product-containing liquid can be produced, for example, on a mass production basis.
  • a device that performs media grinding such as a ball mill physically destroys the void structure of the gel during grinding
  • a cavitation type grinding device such as a homogenizer
  • the relatively weakly bonded porous particle bonding surface already contained is peeled off with a high-speed shearing force.
  • pulverizing the porous gel a new sol three-dimensional structure is obtained, and the three-dimensional structure retains a void structure having a certain range of particle size distribution, for example, in the formation of a coating film.
  • the void structure can be re-formed by deposition during coating and drying.
  • the conditions for the pulverization are not particularly limited.
  • the gel can be pulverized without volatilizing the solvent by instantaneously applying a high-speed flow.
  • the work amount is excessive, for example, the sol particles are finer than the desired particle size distribution, and the void size deposited after coating / drying may become fine and may not satisfy the desired porosity. .
  • the pulverization of the porous body it is preferable to control the pulverization of the porous body while measuring the shear viscosity of the liquid.
  • a specific method for example, in the middle of the pulverization step, a method of adjusting a sol solution that achieves both desired shear viscosity and extremely excellent uniformity, the in-line shear viscosity of the solution is monitored, and the pulverization is performed. There is a method of feeding back to the stage. Thereby, it is possible to produce a gel pulverized product-containing liquid having both desired shear viscosity and extremely excellent uniformity. For this reason, for example, the characteristics of the gel pulverized product-containing liquid can be controlled according to the application.
  • the ratio of the residual silanol groups contained in the pulverized product is not particularly limited, for example, the range exemplified for the silicon compound gel after the aging treatment It is the same.
  • a classification step may be further performed after at least one of the pulverization steps (the first pulverization step and the second pulverization step).
  • the particles of the porous gel are classified.
  • the “classification” refers to, for example, sorting the particles of the porous gel according to the particle size.
  • the classification method is not particularly limited, but can be performed using a sieve. In this way, by performing the pulverization process in a plurality of stages, the uniformity is extremely excellent as described above, and therefore, when applied to uses such as an optical member, the appearance can be improved. However, the appearance can be further improved by further performing the classification treatment.
  • the ratio of the pulverized product in the solvent containing the pulverized product after the pulverizing step and the optional classification step is not particularly limited, and examples thereof include the conditions in the gel pulverized product-containing liquid of the present invention described above.
  • the ratio may be, for example, the condition of the solvent itself containing the pulverized product after the pulverization step, or the adjusted condition after the pulverization step and before use as the gel pulverized product-containing liquid. May be.
  • a liquid for example, a suspension
  • the fine pore particles crushed product of gel-like compound
  • a catalyst that chemically bonds the fine pore particles is added to produce the liquid containing the fine pore particles and the catalyst.
  • the amount of the catalyst to be added is not particularly limited, but 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 silicon compound. %.
  • the catalyst may be, for example, a catalyst that promotes cross-linking between the microporous particles.
  • the fine pore particles As a chemical reaction for chemically bonding the fine pore particles, it is preferable to use a dehydration condensation reaction of residual silanol groups contained in silica sol molecules. By promoting the reaction between the hydroxyl groups of the silanol group with the catalyst, it is possible to form a continuous film that cures the void structure in a short time.
  • the catalyst include a photoactive catalyst and a thermally active catalyst. According to the photoactive catalyst, for example, in the void layer forming step, the fine pore particles can be chemically bonded (for example, crosslinked) without being heated. According to this, for example, in the gap layer forming step, since the shrinkage of the entire gap layer hardly occurs, a higher porosity can be maintained.
  • a substance that generates a catalyst may be used.
  • a substance that generates a catalyst by light may be used, or in addition to or instead of the thermally active catalyst
  • a substance that generates water may be used.
  • the photocatalyst generator is not particularly limited, and examples thereof include a photobase generator (a substance that generates a basic catalyst by light irradiation), a photoacid generator (a substance that generates an acidic catalyst by light irradiation), and the like.
  • a photobase generator is preferred.
  • Examples of the photobase generator include 9-anthrylmethyl N, N-diethylcarbamate (trade name WPBG-018), (E) -1- [3- (2- Hydroxyphenyl) -2-propenoyl] piperidine ((E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, trade name WPBG-027), 1- (anthraquinone-2-yl) ethyl imidazolecarboxy Rate (1- (anthraquinon-2-yl) ethyl imidazolecarboxylate, trade name WPBG-140), 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate (trade name WPBG-165), 1,2-diisopropyl- 3- [bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate (trade name WPBG-266), 1 , 2-dicy
  • the trade names including “WPBG” are trade names of Wako Pure Chemical Industries, Ltd.
  • the photoacid generator include aromatic sulfonium salts (trade name SP-170: ADEKA), triarylsulfonium salts (trade name CPI101A: San Apro), and aromatic iodonium salts (trade name Irgacure 250: Ciba Japan). Company).
  • the catalyst for chemically bonding the fine pore particles is not limited to the photoactive catalyst and the photocatalyst generator, and may be a thermal active catalyst or a thermal catalyst generator, for example.
  • the catalyst for chemically bonding the fine pore particles examples include base catalysts such as potassium hydroxide, sodium hydroxide and ammonium hydroxide, and acid catalysts such as hydrochloric acid, acetic acid and oxalic acid. Of these, base catalysts are preferred.
  • the catalyst or catalyst generator for chemically bonding the fine pore particles is added to a sol particle liquid (for example, suspension) containing the pulverized material (fine pore particles), for example, immediately before coating. Alternatively, it can be used as a mixed solution in which the catalyst or the catalyst generator is mixed with a solvent.
  • the mixed liquid is, for example, a coating liquid dissolved by directly adding to the sol particle liquid, a solution in which the catalyst or catalyst generator is dissolved in a solvent, or a dispersion in which the catalyst or catalyst generator is dispersed in a solvent.
  • the solvent is not particularly limited, and examples thereof include water and a buffer solution.
  • the method for producing the silicone porous body includes, for example, a precursor forming step of forming a precursor of the silicone porous body using the gel pulverized material-containing liquid of the present invention, and the gel pulverization included in the precursor It includes a bonding step for chemically bonding the pulverized material-containing liquids together.
  • the precursor can also be referred to as a coating film, for example.
  • a porous structure having the same function as an air layer is formed.
  • the reason is estimated as follows, for example, but the present invention is not limited to this estimation.
  • the gel pulverized product-containing liquid of the present invention used in the method for producing the porous silicon body includes the pulverized product of the silicon compound gel
  • the three-dimensional structure of the gel-like silica compound is dispersed in the three-dimensional basic structure. It has become a state. Therefore, in the method for producing a porous silicone body, for example, when the precursor (for example, coating film) is formed using the gel pulverized product-containing liquid, the three-dimensional basic structure is deposited, and the three-dimensional basic structure is deposited. A void structure based on the structure is formed.
  • a new three-dimensional structure formed from the pulverized product of the three-dimensional basic structure, which is different from the three-dimensional structure of the silicon compound gel is formed.
  • the said new three-dimensional structure is fixed.
  • the said silicone porous body obtained by the manufacturing method of the said silicone porous body is a structure which has a space
  • the silicone porous body obtained by the present invention can be used for products in a wide range of fields such as a heat insulating material, a sound absorbing material, an optical member, an ink image-receiving layer, etc.
  • a laminated film can be produced.
  • the method for producing the porous silicone body can use the explanation of the gel pulverized product-containing liquid of the present invention.
  • the gel pulverized product-containing liquid of the present invention is applied onto the substrate.
  • the gel pulverized product-containing liquid of the present invention is applied, for example, on a base material, and after the coating film is dried, the pulverized product is chemically bonded (for example, crosslinked) by the bonding step. It is possible to continuously form a void layer having a film strength above a certain level.
  • the coating amount of the gel pulverized product-containing liquid on the substrate is not particularly limited, and can be appropriately set according to, for example, the desired thickness of the porous silicone body.
  • the amount of the gel pulverized product-containing liquid applied to the substrate is, for example, the pulverized product per 1 m 2 of the substrate. 0.01 to 60000 ⁇ g, 0.1 to 5000 ⁇ g, and 1 to 50 ⁇ g.
  • the preferable coating amount of the gel pulverized product-containing liquid is, for example, related to the concentration of the liquid, the coating method, etc., and thus it is difficult to define it uniquely. It is preferable to do.
  • the porous body precursor may be subjected to a drying treatment.
  • a drying treatment for example, not only the solvent (the solvent contained in the gel pulverized product-containing liquid) in the precursor of the porous body is removed, but also the sol particles are settled and deposited during the drying treatment.
  • the purpose is to form a structure.
  • the drying treatment temperature is, for example, 50 to 250 ° C., 60 to 150 ° C., 70 to 130 ° C.
  • the drying treatment time is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, 0 .3-3 minutes.
  • the drying process temperature and time are preferably lower and shorter in relation to, for example, continuous productivity and high porosity.
  • the substrate is a resin film
  • the substrate is extended in a drying furnace by being close to the glass transition temperature of the substrate, and formed immediately after coating. Defects such as cracks may occur in the void structure.
  • the conditions are too loose, for example, since the residual solvent is included at the time of leaving the drying furnace, there is a possibility that defects in appearance such as scratches will occur when rubbing with the roll in the next process. is there.
  • the drying treatment may be, for example, natural drying, heat drying, or vacuum drying.
  • the drying method is not particularly limited, and for example, a general heating means can be used.
  • the heating means include a hot air fan, a heating roll, and a far infrared heater.
  • heat drying when it is premised on industrial continuous production, it is preferable to use heat drying.
  • a solvent having a low surface tension is preferable for the purpose of suppressing the generation of shrinkage stress accompanying the solvent volatilization during drying and the cracking phenomenon of the void layer (the silicone porous body).
  • the solvent include, but are not limited to, lower alcohols typified by isopropyl alcohol (IPA), hexane, perfluorohexane, and the like.
  • the substrate is not particularly limited, for example, a thermoplastic resin substrate, a glass substrate, an inorganic substrate typified by silicon, a plastic molded with a thermosetting resin, an element such as a semiconductor, A carbon fiber-based material typified by carbon nanotube can be preferably used, but is not limited thereto.
  • the form of the substrate include a film and a plate.
  • the thermoplastic resin include polyethylene terephthalate (PET), acrylic, cellulose acetate propionate (CAP), cycloolefin polymer (COP), triacetate (TAC), polyethylene naphthalate (PEN), polyethylene (PE), and polypropylene. (PP).
  • the bonding step is a step of chemically bonding the pulverized materials contained in the porous body precursor (coating film).
  • the bonding step for example, the three-dimensional structure of the pulverized material in the precursor of the porous body is fixed.
  • high temperature treatment at 200 ° C. or higher induces dehydration condensation of silanol groups and formation of siloxane bonds.
  • the bonding step of the present invention by reacting various additives that catalyze the above dehydration condensation reaction, for example, when the substrate is a resin film, the substrate is not damaged, and the temperature is around 100 ° C.
  • the void structure can be continuously formed and fixed at a relatively low drying temperature and a short processing time of less than a few minutes.
  • the method of chemically bonding is not particularly limited, and can be appropriately determined according to, for example, the type of the silicon compound gel.
  • the chemical bonding can be performed by, for example, chemical cross-linking between the pulverized products, and, for example, inorganic particles such as titanium oxide are added to the pulverized product.
  • inorganic particles such as titanium oxide are added to the pulverized product.
  • a biocatalyst such as an enzyme is supported, a site other than the catalytic active site and the pulverized product may be chemically crosslinked.
  • the present invention can be applied to, for example, not only a void layer (silicone porous body) formed by the sol particles but also an organic-inorganic hybrid void layer, a host guest void layer, and the like, but is not limited thereto.
  • the bonding step can be performed, for example, by a chemical reaction in the presence of a catalyst according to the type of pulverized product of the silicon compound gel.
  • a catalyst according to the type of pulverized product of the silicon compound gel.
  • the chemical reaction in the present invention it is preferable to use a dehydration condensation reaction of residual silanol groups contained in the pulverized product of the silicon compound gel.
  • the catalyst include base 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 dehydration condensation reaction is particularly preferably a base catalyst.
  • a photoacid generating catalyst, a photobase generating catalyst, or the like that exhibits catalytic activity when irradiated with light can be preferably used.
  • light for example, ultraviolet rays
  • the catalyst is preferably added to the sol particle liquid containing the pulverized product immediately before coating, or used as a mixed liquid in which the catalyst is mixed with a solvent.
  • the mixed liquid may be, for example, a coating liquid that is directly added and dissolved in 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 solvent is not particularly limited, and examples thereof include water and a buffer solution as described above.
  • a crosslinking aid for indirectly bonding the crushed gels may be added to the gel-containing liquid of the present invention.
  • This crosslinking aid enters between the particles (the pulverized product), and the particles and the crosslinking aid interact or bond with each other, so that it is possible to bind particles that are slightly apart in distance. The strength can be increased efficiently.
  • a polycrosslinked silane monomer is preferable.
  • the multi-crosslinked silane monomer has, for example, an alkoxysilyl group having 2 or more and 3 or less, the chain length between alkoxysilyl groups may be 1 to 10 carbon atoms, and an element other than carbon May also be included.
  • crosslinking aid examples include bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triethoxysilyl) propane, bis (Trimethoxysilyl) propane, bis (triethoxysilyl) butane, bis (trimethoxysilyl) butane, bis (triethoxysilyl) pentane, bis (trimethoxysilyl) pentane, bis (triethoxysilyl) hexane, bis (tri Methoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) -N-butyl-N-propyl-ethane-1
  • the chemical reaction in the presence of the catalyst is, for example, light irradiation or heating on the coating film containing the catalyst or the catalyst generator previously added to the gel pulverized product-containing liquid, or on the coating film. It can be carried out by light irradiation or heating after spraying the catalyst, or by light irradiation or heating while spraying the catalyst or catalyst generator.
  • the catalyst is a photoactive catalyst
  • the porous silicon body can be formed by chemically bonding the fine pore particles by light irradiation.
  • the silicone porous body can be formed by chemically bonding the fine pore particles by heating.
  • Light irradiation amount in the irradiation (energy) is not particularly limited, @ in 360nm terms, for example, 200 ⁇ 800mJ / cm 2, 250 ⁇ 600mJ / cm 2 or 300 ⁇ 400mJ / cm 2,. From the viewpoint of preventing the irradiation amount from being insufficient and the decomposition due to light absorption of the catalyst generator from proceeding and preventing the effect from becoming insufficient, an integrated light amount of 200 mJ / cm 2 or more is good. Further, from the viewpoint of preventing the base material under the void layer from being damaged and generating thermal wrinkles, an integrated light amount of 800 mJ / cm 2 or less is good.
  • the wavelength of light in the light irradiation is not particularly limited, but is, for example, 200 to 500 nm, 300 to 450 nm.
  • the light irradiation time in the light irradiation is not particularly limited, and is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, or 0.3 to 3 minutes.
  • the conditions for the heat treatment are not particularly limited, and the heating temperature is, for example, 50 to 250 ° C., 60 to 150 ° C., 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.
  • a solvent having a low surface tension is preferable for the purpose of suppressing the generation of shrinkage stress accompanying the solvent volatilization during drying and the cracking phenomenon of the void layer.
  • examples thereof include, but are not limited to, lower alcohols typified by isopropyl alcohol (IPA), hexane, perfluorohexane, and the like.
  • the silicone porous body manufactured in this way may be called “the silicone porous body of this invention” below.
  • the manufacturing method of the silicone porous body of this invention is not limited above.
  • the silicone porous body of this invention is 1 type of the high porosity layer of this invention, or the high porosity porous body of this invention, for example.
  • the adhesive peel strength to the resin film can be improved by the strength improving step (aging step).
  • the strength improvement process aging process
  • the temperature in the aging step is, for example, 40 to 80 ° C., 50 to 70 ° C., 55 to 65 ° C.
  • the reaction time is, for example, 5 to 30 hours, 7 to 25 hours, or 10 to 20 hours.
  • the adhesive peel strength can be improved while suppressing the shrinkage of the silicone porous body, and both high porosity and strength can be achieved.
  • the catalyst contained in the silicone porous body of the present invention causes chemical bonding (for example, cross-linking reaction) between the microporous particles. It is considered that the strength is improved by proceeding further.
  • the catalyst contained in the porous silicone material of the present invention is not particularly limited.
  • the catalyst used in the bonding step may be used, or the photobase generation catalyst used in the bonding step may be a base generated by light irradiation.
  • the photoacid generating catalyst used in the binding step may be an acidic substance generated by light irradiation or the like.
  • this description is illustrative and does not limit the present invention.
  • an adhesive layer may be further formed on the silicone porous body of the present invention (adhesive layer forming step).
  • the adhesive layer may be formed by applying (coating) a pressure-sensitive adhesive or an adhesive onto the silicone porous body of the present invention.
  • the adhesive layer side such as an adhesive tape in which the adhesive layer is laminated on a base material is bonded onto the silicone porous body of the present invention, whereby the above-mentioned silicone porous body of the present invention is An adhesive layer may be formed.
  • the base material such as the adhesive tape may be left as it is or may be peeled off from the adhesive layer.
  • adheresive and “adhesive layer” refer to, for example, an agent or layer premised on re-peeling of the adherend.
  • adheresive and “adhesive layer” refer to, for example, an agent or a layer that does not assume re-peeling of the adherend.
  • pressure-sensitive adhesive and “adhesive” are not necessarily clearly distinguished, and “pressure-sensitive adhesive layer” and “adhesive layer” are not necessarily clearly distinguished.
  • the adhesive or adhesive which forms the said adhesive layer is not specifically limited, For example, a general adhesive or adhesive etc. can be used.
  • the pressure-sensitive adhesive or adhesive examples include acrylic, vinyl alcohol, silicone, polyester, polyurethane, and polyether polymer adhesives, rubber adhesives, and the like.
  • an adhesive composed of a water-soluble crosslinking agent of vinyl alcohol polymers such as glutaraldehyde, melamine, and oxalic acid can be used.
  • These pressure-sensitive adhesives and adhesives may be used alone or in combination (for example, mixing, lamination, etc.).
  • the thickness of the adhesive layer is not particularly limited, and is, for example, 0.1 to 100 ⁇ m, 5 to 50 ⁇ m, 10 to 30 ⁇ m, or 12 to 25 ⁇ m.
  • the silicone porous body of the present invention may be reacted with the adhesive layer to form an intermediate layer disposed between the silicone porous body of the present invention and the adhesive layer (intermediate layer). Forming step).
  • the intermediate layer for example, the silicone porous body of the present invention and the adhesive layer are difficult to peel off.
  • the reason (mechanism) is unknown, but is presumed to be due to, for example, the throwing property (throwing effect) of the intermediate layer.
  • the anchoring property (an anchoring effect) is that the interface is firmly fixed in the vicinity of the interface between the void layer and the intermediate layer because the intermediate layer is embedded in the void layer. A phenomenon (effect).
  • the reaction between the silicone porous body of the present invention and the adhesive layer is not particularly limited, but may be a reaction by catalytic action, for example.
  • the catalyst may be, for example, a catalyst contained in the porous silicone body of the present invention.
  • the catalyst used in the coupling step may be used
  • the photobase generation catalyst used in the coupling step is a basic substance generated by light irradiation
  • the photoacid generation catalyst used in the coupling step is light.
  • An acidic substance generated by irradiation may be used.
  • the reaction between the porous silicone body of the present invention and the adhesive layer may be, for example, a reaction in which a new chemical bond is generated (for example, a crosslinking reaction).
  • the reaction temperature is, for example, 40 to 80 ° C., 50 to 70 ° C., 55 to 65 ° C.
  • the reaction time is, for example, 5 to 30 hours, 7 to 25 hours, or 10 to 20 hours.
  • middle layer formation process may serve as the said intensity
  • porous silicone body of the present invention may be further laminated with another film (layer) to form a laminated structure including the porous structure.
  • each component may be laminated via, for example, a pressure-sensitive adhesive or an adhesive.
  • the lamination may be performed by continuous processing using a long film (so-called Roll to Roll, etc.). May be laminated with batch processing.
  • FIG. 2 although forming the said silicone porous body and showing the process of bonding and winding up a protective film, when laminating
  • the illustrated film forming method is merely an example, and the present invention is not limited thereto.
  • FIG. 1 is a cross-sectional view schematically showing an example of steps in the method for forming the silicone porous body on the substrate.
  • the formation method of the said porous silicone body is the coating process (1) which coats the said gel ground material containing liquid 20 '' of the said this invention on the base material 10, The gel ground material containing liquid 20 ''.
  • the porous silicone body 20 can be formed on the substrate 10 as shown.
  • the method for forming a porous silicone body may or may not include steps other than the steps (1) to (3) as appropriate.
  • the coating method of the gel pulverized product-containing liquid 20 '' is not particularly limited, and a general coating method can be adopted.
  • the coating method include a slot die method, a reverse gravure coating method, a micro gravure method (micro gravure coating method), a dip method (dip coating method), a spin coating method, a brush coating method, a roll coating method, and flexographic printing.
  • the extrusion coating method, the curtain coating method, the roll coating method, the micro gravure coating method and the like are preferable from the viewpoints of productivity, coating film smoothness, and the like.
  • the coating amount of the gel pulverized product-containing liquid 20 ′′ is not particularly limited, and can be appropriately set so that, for example, the thickness of the porous structure (silicone porous body) 20 is appropriate.
  • the thickness of the porous structure (silicone porous body) 20 is not particularly limited, and is as described above, for example.
  • the gel pulverized product-containing liquid 20 ′′ is dried (that is, the dispersion medium contained in the gel pulverized product-containing liquid 20 ′′ is removed) to form a coating film (precursor layer) 20 ′.
  • the conditions for the drying treatment are not particularly limited and are as described above.
  • the coating film 20 ′ containing the catalyst for example, photoactive catalyst, photocatalyst generator, thermal active catalyst or thermal catalyst generator
  • the catalyst for example, photoactive catalyst, photocatalyst generator, thermal active catalyst or thermal catalyst generator
  • Irradiation or heating is performed to chemically bond (for example, crosslink) the pulverized materials in the coating film (precursor) 20 ′ to form the porous silicone body 20.
  • the light irradiation or heating conditions in the chemical treatment step (3) are not particularly limited and are as described above.
  • FIG. 2 schematically shows an example of a coating apparatus using the slot die method and a method for forming the porous silicone material using the same.
  • FIG. 2 is a cross-sectional view, hatching is omitted for easy viewing.
  • each step in the method using this apparatus is performed while the substrate 10 is conveyed in one direction by a roller.
  • the conveyance speed is not particularly limited, and is, for example, 1 to 100 m / min, 3 to 50 m / min, or 5 to 30 m / min.
  • a coating step (1) is performed in which the substrate roll 10 is fed from the feed roller 101 and conveyed, and the coating roll 102 applies the gel pulverized product-containing liquid 20 ′′ of the present invention to the substrate.
  • the process proceeds to the drying step (2).
  • a preliminary drying process is performed after a coating process (1) and prior to a drying process (2).
  • the preliminary drying step can be performed at room temperature without heating.
  • the heating means 111 is used.
  • the heating means 111 as described above, a hot air fan, a heating roll, a far infrared heater, or the like can be used as appropriate.
  • the drying step (2) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed.
  • the chemical treatment step (3) is performed in the chemical treatment zone 120.
  • the chemical treatment step (3) for example, when the dried coating film 20 ′ includes a photoactive catalyst, light irradiation is performed by lamps (light irradiation means) 121 disposed above and below the base material 10.
  • lamps (light irradiation means) 121 disposed above and below the base material 10.
  • a hot air fan 121 disposed above and below the substrate 10 using a hot air fan (heating means) instead of the lamp (light irradiation device) 121.
  • the pulverized material in the coating film 20 ′ is chemically bonded to each other, and the porous silicone body 20 is cured and strengthened.
  • the laminated body in which the porous silicone body 20 is formed on the substrate 10 is wound up by the winding roll 105.
  • the porous structure 20 of the laminate is covered and protected with a protective sheet fed from a roll 106.
  • the protective sheet instead of the protective sheet, another layer formed of a long film may be laminated on the porous structure 20.
  • FIG. 3 schematically shows an example of a micro gravure method (micro gravure coating method) coating apparatus and a method for forming the porous structure using the same.
  • the hatch is abbreviate
  • each step in the method using this apparatus is performed while the substrate 10 is conveyed in one direction by a roller, as in FIG.
  • the conveyance speed is not particularly limited, and is, for example, 1 to 100 m / min, 3 to 50 m / min, or 5 to 30 m / min.
  • Application of the gel pulverized product-containing liquid 20 ′′ is performed using a liquid reservoir 202, a doctor (doctor knife) 203, and a micro gravure 204 as shown in the figure.
  • the gel pulverized product-containing liquid 20 ′′ stored in the liquid reservoir 202 is attached to the surface of the microgravure 204, and further controlled to a predetermined thickness by the doctor 203, while being controlled by the microgravure 204. Apply to the surface of the material 10.
  • the microgravure 204 is merely an example, and the present invention is not limited to this, and any other coating means may be used.
  • a drying step (2) is performed. Specifically, as shown in the drawing, the base material 10 coated with the gel pulverized product-containing liquid 20 ′′ is transported into the oven zone 210, heated by the heating means 211 in the oven zone 210 and dried.
  • the heating means 211 may be the same as that shown in FIG. Further, for example, by dividing the oven zone 210 into a plurality of sections, the drying step (2) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed.
  • the chemical treatment step (3) is performed in the chemical treatment zone 220.
  • the chemical treatment step (3) for example, when the dried coating film 20 ′ includes a photoactive catalyst, light irradiation is performed by lamps (light irradiation means) 221 disposed above and below the substrate 10.
  • lamps (light irradiation means) 221 disposed above and below the substrate 10.
  • a hot air fan (heating means) is used instead of the lamp (light irradiation device) 221 and is arranged below the base material 10 ( The substrate 10 is heated by the heating means 221.
  • the pulverized material in the coating film 20 ′ is chemically bonded to each other, and the porous silicone body 20 is formed.
  • the laminated body in which the silicone porous body 20 is formed on the substrate 10 is wound up by the winding roll 251. Thereafter, for example, another layer may be laminated on the laminate. Further, before the laminate is taken up by the take-up roll 251, for example, another layer may be laminated on the laminate.
  • FIGS. 4 to 6 show another example of the continuous treatment process in the method for forming a porous silicone body of the present invention.
  • this method is performed except that a chemical treatment step (for example, a crosslinking treatment step) (3) for forming the silicone porous body 20 is followed by a strength improving step (aging step) (4).
  • a chemical treatment step for example, a crosslinking treatment step (3) for forming the silicone porous body 20
  • a strength improving step (aging step) (4) Is the same as the method shown in FIGS.
  • the strength improving step (aging step) (4) the strength of the silicone porous body 20 is improved to obtain a silicone porous body 21 with improved strength.
  • the strength improving step (aging step) (4) is not particularly limited, and is as described above, for example.
  • FIG. 5 is a schematic view showing another example of the coating apparatus of the slot die method and the method of forming the silicone porous body using the slot die method.
  • this coating apparatus has a strength improving zone (aging zone) 130 for performing a strength improving step (aging step) (4) immediately after the chemical processing zone 120 for performing the chemical processing step (3).
  • the strength improvement step (aging step) (4) is performed in the strength improvement zone (aging zone) 130 to improve the adhesive peel strength of the silicone porous body 20 to the resin film 10.
  • the porous silicone body 21 with improved adhesive peel strength is formed.
  • the strength improving step (aging step) (4) may be performed, for example, by heating the porous silicone body 20 as described above using the hot air fans (heating means) 131 disposed above and below the base material 10. .
  • heating temperature, time, etc. are not specifically limited, For example, it is as above-mentioned.
  • the laminated film in which the porous silicon body 21 is formed on the substrate 10 is wound up by the winding roll 105.
  • FIG. 6 is a schematic view showing another example of the coating apparatus of the micro gravure method (micro gravure coating method) and the method for forming the porous structure using the same, as shown in FIG.
  • this coating apparatus has a strength improving zone (aging zone) 230 for performing a strength improving step (aging step) (4) immediately after the chemical processing zone 220 for performing chemical processing step (3).
  • the strength improvement step (aging step) (4) is performed in the strength improvement zone (aging zone) 230 to improve the adhesive peel strength of the porous silicone body 20 to the resin film 10.
  • the porous silicone body 21 with improved adhesive peel strength is formed.
  • the strength improving step (aging step) (4) may be performed, for example, by heating the porous silicone body 20 as described above using the hot air blowers (heating means) 231 disposed above and below the base material 10. . Although heating temperature, time, etc. are not specifically limited, For example, it is as above-mentioned. Thereafter, similarly to FIG. 3, the laminated film in which the silicone porous body 21 is formed on the substrate 10 is wound up by the winding roll 251.
  • FIGS. 7 to 9 show another example of the continuous treatment process in the method of forming the porous silicone body of the present invention.
  • this method applies the adhesive layer 30 on the silicone porous body 20 after the chemical treatment step (for example, the crosslinking treatment step) (3) for forming the silicone porous body 20.
  • An adhesive layer coating step adheresive layer forming step) (4), and an intermediate layer forming step (5) in which the silicone porous body 20 is reacted with the adhesive layer 30 to form the intermediate layer 22.
  • the method of FIGS. 7 to 9 is the same as the method shown in FIGS.
  • the intermediate layer forming step (5) also serves as a step of improving the strength of the silicone porous body 20 (strength improving step).
  • the silicone porous body 20 The porous silicon body 21 is improved in strength.
  • this invention is not limited to this,
  • the silicone porous body 20 does not need to change after an intermediate
  • the adhesive layer coating step (adhesive layer forming step) (4) and the intermediate layer forming step (5) are not particularly limited, and are as described above, for example.
  • FIG. 8 is a schematic view showing still another example of the coating apparatus of the slot die method and the method of forming the silicone porous body using the same.
  • this coating apparatus has an adhesive layer coating zone 130a for performing the adhesive layer coating step (4) immediately after the chemical processing zone 120 for performing the chemical processing step (3).
  • the intermediate layer forming zone (aging zone) 130 disposed immediately after the adhesive layer coating zone 130a is obtained by the hot air blower (heating means) 131 disposed above and below the base material 10, and the strength of FIG.
  • the same heat treatment as in the improvement zone (aging zone) 130 can be performed. That is, in the apparatus of FIG.
  • the adhesive or adhesive is applied on the silicone porous body 20 by the adhesive layer coating means 131a in the adhesive layer coating zone 130a.
  • An adhesive layer coating process (adhesive layer forming process) (4) for applying (coating) and forming the adhesive layer 30 is performed. Further, as described above, instead of application (coating) of the pressure-sensitive adhesive or adhesive, bonding (sticking) such as a pressure-sensitive adhesive tape having the adhesive layer 30 may be used. Further, the intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming zone (aging zone) 130, and the porous silicon body 20 and the adhesive layer 30 are reacted to form the intermediate layer 22.
  • the silicone porous body 20 becomes the silicone porous body 21 with improved strength.
  • the heating temperature, time, etc. by the hot air fan (heating means) 131 are not specifically limited, For example, it is as above-mentioned.
  • FIG. 9 is a schematic diagram showing still another example of a micro gravure method (micro gravure coating method) coating apparatus and a method for forming the porous structure using the same.
  • this coating apparatus has an adhesive layer coating zone 230a for performing the adhesive layer coating step (4) immediately after the chemical processing zone 220 for performing the chemical processing step (3).
  • the intermediate layer forming zone (aging zone) 230 disposed immediately after the adhesive layer coating zone 230a is obtained from the strength shown in FIG.
  • the same heat treatment as that of the improvement zone (aging zone) 230 can be performed. That is, in the apparatus of FIG.
  • the adhesive or adhesive is applied on the silicone porous body 20 by the adhesive layer coating means 231a in the adhesive layer coating zone 230a.
  • An adhesive layer coating process (adhesive layer forming process) (4) for applying (coating) and forming the adhesive layer 30 is performed. Further, as described above, instead of application (coating) of the pressure-sensitive adhesive or adhesive, bonding (sticking) such as a pressure-sensitive adhesive tape having the adhesive layer 30 may be used. Further, an intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming zone (aging zone) 230, and the porous silicon body 20 and the adhesive layer 30 are reacted to form the intermediate layer 22. Further, as described above, in this step, the silicone porous body 20 becomes the silicone porous body 21 with improved strength.
  • the heating temperature, time, and the like by the hot air fan (heating means) 231 are not particularly limited, and are as described above, for example.
  • the functional porous body of the present invention has, for example, a scratch resistance of 60 to 100% by Bencot (registered trademark) indicating the film strength, and a folding resistance of 100 or more by the MIT test indicating flexibility. Although there may be, it is not limited to this.
  • the functional porous body of the present invention uses, for example, a pulverized product of the porous gel, the three-dimensional structure of the porous gel is destroyed, and a new three-dimensional structure different from the porous gel is obtained. Is formed.
  • the functional porous body of the present invention is a layer in which a new pore structure (new void structure) that cannot be obtained by the layer formed from the porous gel is formed, and thus the porosity is reduced.
  • a high nanoscale functional porous body can be formed.
  • the functional porous body of the present invention for example, when the functional porous body is a silicone porous body, for example, chemically bond the pulverized products to each other while adjusting the number of siloxane bond functional groups of the silicon compound gel.
  • the functional porous body of the present invention includes, for example, the functional
  • the porous body is a functional porous body
  • the structure has voids, but sufficient strength and flexibility can be maintained. Therefore, according to this invention, a functional porous body can be provided to various objects easily and simply.
  • the functional porous body of the present invention can be used as, for example, a heat insulating material, a sound absorbing material, a scaffold for regenerative medicine, a dew condensation preventing material, an optical member, etc., instead of an air layer.
  • the functional porous body of the present invention includes, for example, a pulverized product of a porous gel as described above, and the pulverized product is chemically bonded to each other.
  • the form of chemical bonding (chemical bonding) between the pulverized products is not particularly limited, and specific examples of the chemical bonding include, for example, cross-linking.
  • the method of chemically bonding the pulverized products will be described in detail in the method for producing the functional porous body described later.
  • the cross-linking is, for example, a siloxane bond.
  • the siloxane bond include T2 bond, T3 bond, and T4 bond shown below.
  • T2 bond T2 bond
  • T3 bond T4 bond
  • the silicone porous body of the present invention may have any one kind of bond, any two kinds of bonds, or all three kinds of bonds. Also good.
  • the siloxane bonds the greater the ratio of T2 and T3, the more flexible and the expected properties of the gel can be expected, but the film strength becomes weaker.
  • the T4 ratio in the siloxane bond is large, the film strength is easily expressed, but the void size becomes small and the flexibility becomes brittle. For this reason, for example, it is preferable to change the ratio of T2, T3, and T4 according to the application.
  • the contained silicon atoms have a siloxane bond.
  • the proportion of unbonded silicon atoms (that is, residual silanol) in the total silicon atoms contained in the porous silicone material is, for example, less than 50%, 30% or less, or 15% or less.
  • the functional porous body of the present invention has a pore structure, and the pore size refers to the major axis diameter of the major axis and minor axis diameter of the void (hole). .
  • the pore size is, for example, 5 nm to 200 nm.
  • the lower limit of the void size is, for example, 5 nm or more, 10 nm or more, 20 nm or more, and the upper limit thereof is, for example, 1000 ⁇ m or less, 500 ⁇ m or less, 100 ⁇ m or less, and the range thereof is, for example, 5 nm to 1000 ⁇ m, 10 nm. ⁇ 500 ⁇ m, 20 nm ⁇ 100 ⁇ m. Since a preferable void size is determined depending on the use of the void structure, it is necessary to adjust the void size to a desired void size according to the purpose, for example.
  • the void size can be evaluated by the following method, for example.
  • the void size can be quantified by a BET test method. Specifically, 0.1 g of a sample (functional porous body of the present invention) was put into a capillary of a specific surface area measuring apparatus (Micromeritic: ASAP2020), and then dried under reduced pressure at room temperature for 24 hours. Degas the gas in the void structure. The adsorption isotherm is drawn by adsorbing nitrogen gas to the sample, and the pore distribution is obtained. Thereby, the gap size can be evaluated.
  • the functional porous body of the present invention has a scratch resistance of 60 to 100% due to Bencot (registered trademark) indicating film strength. Since the present invention has such a film strength, for example, it is excellent in scratch resistance in various processes.
  • the present invention has, for example, scratch resistance in a production process when winding the product after forming the functional porous body and handling a product film.
  • the functional porous body of the present invention uses, for example, a catalytic reaction in a heating step described later, instead of reducing the porosity, and the particle size of the pulverized product of the silicon compound gel and the pulverized product. It is possible to increase the bonding strength of the neck portions that are bonded to each other. Thereby, the functional porous body of the present invention can give a certain level of strength to, for example, a void structure that is inherently fragile.
  • the lower limit of the scratch resistance is, for example, 60% or more, 80% or more, 90% or more, and the upper limit thereof is, for example, 100% or less, 99% or less, 98% or less, and the range is For example, they are 60 to 100%, 80 to 99%, 90 to 98%.
  • the scratch resistance can be measured by, for example, the following method.
  • a void layer (functional porous body of the present invention) coated and formed on an acrylic film is sampled in a circular shape having a diameter of about 15 mm.
  • silicon is identified with fluorescent X-rays (manufactured by Shimadzu Corporation: ZSX Primus II), and the Si coating amount (Si 0 ) is measured.
  • the gap layer on the acrylic film is cut to 50 mm ⁇ 100 mm from the vicinity sampled, and fixed to a glass plate (thickness 3 mm). Perform dynamic tests.
  • the sliding condition is a weight of 100 g and 10 reciprocations.
  • the residual amount of Si (Si 1 ) after the scratch test is measured by sampling and fluorescent X measurement in the same manner as in (1) above from the gap layer after sliding.
  • the silicone porous body of the present invention has, for example, a folding resistance of 100 times or more according to the MIT test showing flexibility. Since the present invention has such flexibility, for example, it is excellent in handleability during winding or use during production.
  • the lower limit of the folding endurance number is, for example, 100 times or more, 500 times or more, 1000 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 10000 times, 500 times to 10000 times, 1000 times to 10000 times.
  • the flexibility means, for example, ease of deformation of the substance.
  • the folding endurance by the MIT test can be measured by the following method, for example.
  • the void layer (the functional porous body of the present invention) is cut into a strip of 20 mm ⁇ 80 mm, and then attached to an MIT folding tester (manufactured by Tester Sangyo Co., Ltd .: BE-202), and a load of 1.0 N is applied. .
  • the chuck part that embeds the gap layer uses R 2.0 mm, performs the folding endurance up to 10,000 times, and sets the number of times when the gap layer is broken as the number of folding endurances.
  • the film density showing the porosity is not particularly limited, and the lower limit thereof is, for example, 1 g / cm 3 or more, 5 g / cm 3 or more, 10 g / cm 3 or more, 15 g / cm 3.
  • the upper limit is, for example, 50 g / cm 3 or less, 40 g / cm 3 or less, 30 g / cm 3 or less, 2.1 g / cm 3 or less, and the range is, for example, 5 to 50 g / cm 3. 10 to 40 g / cm 3 , 15 to 30 g / cm 3 , and 1 to 2.1 g / cm 3 .
  • the film density can be measured by the following method, for example.
  • the functional porous body of the present invention only needs to have a pore structure (porous structure) as described above, and may be, for example, an open cell structure in which the pore structure is continuous.
  • the open cell structure means, for example, that the porous structure is three-dimensionally connected in the functional porous body, and it can be said that the internal voids of the porous structure are continuous.
  • the porous body has an open cell structure, it is possible to increase the porosity occupied in the bulk.
  • closed cells such as hollow silica are used, the open cell structure cannot be formed.
  • the functional porous body of the present invention has a three-dimensional dendritic structure because the sol particles (pulverized porous gel forming the sol) have a coating film (pulverized porous gel). In the sol coating film containing matter), the dendritic particles settle and deposit, whereby it is possible to easily form an open cell structure.
  • the functional porous body of the present invention more preferably forms a monolith structure in which the open cell structure has a plurality of pore distributions.
  • the monolith structure refers to, for example, a structure in which nano-sized fine voids exist and a hierarchical structure in which the nano-voids are gathered as an open cell structure.
  • the monolith structure for example, while providing film strength with fine voids, high porosity can be imparted with coarse open-cell voids, and both film strength and high porosity can be achieved.
  • the monolith structure can be formed by controlling the particle size distribution of the pulverized product to a desired size.
  • the tear crack generation elongation showing flexibility is not particularly limited, and the lower limit thereof is, for example, 0.1% or more, 0.5% or more, 1% or more, The upper limit is, for example, 3% or less.
  • the range of the tear crack occurrence elongation is, for example, 0.1 to 3%, 0.5 to 3%, and 1 to 3%.
  • the tear crack elongation rate can be measured, for example, by the following method.
  • the haze showing transparency is not particularly limited, and the lower limit thereof is, for example, 0.1% or more, 0.2% or more, 0.3% or more, and the upper limit is For example, it is 10% or less, 5% or less, 3% or less, and the range is, for example, 0.1 to 10%, 0.2 to 5%, or 0.3 to 3%.
  • the haze can be measured by, for example, the following method.
  • the void layer (functional porous body of the present invention) is cut into a size of 50 mm ⁇ 50 mm, and set in a haze meter (Murakami Color Research Laboratory Co., Ltd .: HM-150) to measure haze.
  • the refractive index is generally the ratio of the transmission speed of the wavefront of light in a vacuum to the propagation speed in the medium is called the refractive index of the medium.
  • the refractive index of the porous silicone material of the present invention is not particularly limited, and the upper limit thereof is, for example, 1.3 or less, less than 1.3, 1.25 or less, 1.2 or less, 1.15 or less,
  • the lower limit is, for example, 1.05 or more, 1.06 or more, 1.07 or more, and the range thereof is, for example, 1.05 or more and 1.3 or less, 1.05 or more and less than 1.3, 1.05 or more 1.25 or less, 1.06 or more to less than 1.2, 1.07 or more to 1.15 or less.
  • the refractive index means a refractive index measured at a wavelength of 550 nm unless otherwise specified.
  • the measuring method of a refractive index is not specifically limited, For example, it can measure with the following method.
  • the thickness of the functional porous body of the present invention is not particularly limited, and the lower limit thereof is, for example, 0.05 ⁇ m or more and 0.1 ⁇ m or more, and the upper limit thereof is, for example, 1000 ⁇ m or less, 100 ⁇ m or less, and the range thereof. Are, for example, 0.05 to 1000 ⁇ m and 0.1 to 100 ⁇ m.
  • the form of the functional porous body of the present invention is not particularly limited, and may be, for example, a film shape or a block shape.
  • the method for producing the functional porous body of the present invention is not particularly limited, and for example, it can be produced by the method for producing the functional porous body shown below.
  • the member containing the functional porous body examples include a heat insulating material, a sound absorbing material, a dew condensation preventing material, and an optical member. These members can be used, for example, by placing them where an air layer is required. The form in particular of these members is not restrict
  • examples of the member including the functional porous body include a scaffold for regenerative medicine.
  • the functional porous body has a porous structure that exhibits the same function as the air layer. Since the voids of the functional porous body are suitable for holding, for example, cells, nutrient sources, air, etc., the porous structure is useful as a scaffold for regenerative medicine, for example.
  • Examples of the member containing the functional porous material include a total reflection member, an ink image receiving material, a single layer AR (decrease reflection), a single layer moth eye, and a dielectric constant material.
  • Example 1 First, gelation of the silicon compound (the following step (1)) and aging step (the following step (2)) were performed to produce a gel (silicone porous body) having a porous structure.
  • the process of this reference example corresponds to the “gel production process” in the method for producing a crushed gel-containing liquid of the present invention.
  • the aging step is optional as described above.
  • the following (3) form control step, (4) solvent replacement step, (5) concentration measurement (concentration management) and concentration adjustment step, and (6) pulverization step were performed to obtain a gel pulverized product-containing liquid.
  • the following (3) form control step was performed as a step different from the following step (1).
  • this invention is not limited to this, For example, you may perform the following (3) form control process in the following process (1).
  • pulverization was performed at a pulverization pressure of 100 MPa.
  • an isobutyl alcohol dispersion gel pulverized product-containing liquid in which nanometer-sized particles (the pulverized product of the gel) were dispersed was obtained.
  • the solid content concentration (gel concentration) of the liquid was measured. 3.01% by weight.
  • the volume average particle diameter of the pulverized product of the gel is 3 to 5 ⁇ m, and the shear viscosity of the liquid is It was 4,000 mPa ⁇ s.
  • the measurement value after the first pulverization step was adopted as it was.
  • the volume average particle diameter of the gel pulverized product was 250 to 350 nm, and the shear viscosity of the liquid was 5 m to 10 mPa ⁇ s.
  • the solid content concentration (gel concentration) of the liquid (gel pulverized product-containing liquid) was measured again, and was 3.01% by weight. It was not changed after the 1st grinding stage (coarse grinding process).
  • the average particle size of the pulverized product (sol particles) of the gel after the first pulverization step and the second pulverization step is determined by a dynamic light scattering nanotrack particle size analyzer (Nikkiso). (Product name: UPA-EX150 type). Further, in this example, the shear viscosity of the liquid after the first pulverization step and the second pulverization step was confirmed with a vibration type viscosity measuring machine (trade name FEM-1000V, manufactured by Seconic). . The same applies to the following examples and comparative examples.
  • the first pulverization step in the solid content (gel) of the gel pulverized product-containing liquid, among the functional groups (silanol groups) of the constituent unit monomer, it contributes to the intragel crosslinked structure.
  • Measurement (calculation) of the ratio of no functional group (residual silanol group) yielded a measurement value of 11 mol%.
  • the ratio of the functional groups (residual silanol groups) that do not contribute to the intra-gel crosslinked structure is determined by measuring solid NMR (Si-NMR) after drying the gel and contributing to the crosslinked structure from the NMR peak ratio. It was measured by a method of calculating the ratio of no remaining silanol groups.
  • Example 2 The (3) form control step described in Example 1 was performed simultaneously with the gel synthesis step (gelation of silicon compound) of (1).
  • the mixed solution described in Example (1) is poured into a stainless steel container in which rectangular parallelepiped partitions having a length of 2 cm, a width of 3 cm, and a height of 5 cm are arranged (1) gelation and (2) an aging step. A shaped mass gel was obtained. The gel of the lump was taken out from each partition of the container without cutting and subjected to the next (4) solvent replacement step as it was. A gel pulverized product-containing liquid was produced in the same manner as Example 1 except for these.
  • the concentration of the gel pulverized product-containing liquid UP was adjusted by vacuum degassing and solvent removal by heating for the purpose of increasing the coating thickness of the high void layer.
  • aggregation of particles was confirmed, and precipitation of the particle solid was confirmed in the liquid after the second pulverization step (nano-pulverization step).
  • Example 1 The results of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 are summarized in Table 1 below.
  • Table 1 As shown in Table 1 below, after the solvent replacement step, before the start of the first pulverization step, the concentration of the liquid containing the gel is adjusted (concentration adjustment step), and the first pulverization step (the first pulverization step) is started.
  • the concentration of the liquid containing the gel was not adjusted after that time, the uniformity of the gel pulverized product-containing liquid obtained after the second pulverization step (nano pulverization step) was extremely excellent. It was.
  • Comparative Example 1 in which the concentration of the liquid containing the gel was not appropriately adjusted, as described above, the liquid became too viscous and pulverization was insufficient, and the gel concentration could not be measured. .
  • Comparative Example 2 in which the concentration UP (concentration adjustment) of the gel pulverized product-containing liquid was performed after the second pulverization step (nano-pulverization step), as described above, after the second pulverization step (nano-pulverization step) Precipitation of particulate solids occurred in this liquid, and a uniform gel pulverized product-containing liquid could not be obtained.
  • the present invention it is possible to provide a method for producing a gel pulverized product-containing liquid capable of forming a high void structure with extremely excellent uniformity even in mass production at an industrial level.
  • the gel pulverized material-containing liquid of the present invention is used, for example, the porous structure is fixed by chemically bonding the pulverized materials to each other, so that the obtained porous structure has a void structure.
  • sufficient strength can be maintained. For this reason, the said porous structure can provide a functional porous body to various objects easily and simply.
  • the porous structure can be industrially used in a wide range of fields such as a heat insulating material, a sound absorbing material, a regenerative medical scaffolding material, a dew condensation prevention material, and an optical member, for example, instead of an air layer. .

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Silicon Compounds (AREA)
  • Colloid Chemistry (AREA)

Abstract

Le but de l'invention est de fournir un procédé de production d'un liquide très homogène contenant un gel pulvérisé. Ce procédé de production d'un liquide contenant un gel pulvérisé comprend une étape de production de gel destinée à produire un gel, une étape de substitution de solvant destinée à remplacer le solvant contenu dans le gel par un autre solvant, et une étape de pulvérisation de gel destinée à pulvériser le gel dans l'autre solvant, le procédé de production d'un gel contenant le gel pulvérisé étant caractérisé en ce que l'étape de pulvérisation est effectuée en une pluralité d'étapes de pulvérisation distinctes, une étape de régulation de la concentration pour réguler la concentration du liquide qui contient le gel est utilisée après l'étape de substitution de solvant et avant le début de la première étape de pulvérisation, et la concentration du liquide qui contient le gel n'est pas régulée après le début de la première étape de pulvérisation.
PCT/JP2017/003076 2016-01-29 2017-01-28 Procédé de production de liquide contenant un gel pulvérisé WO2017131220A1 (fr)

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Citations (6)

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JPH06219717A (ja) * 1992-11-04 1994-08-09 Grace Gmbh 高い細孔容積と大きな孔直径を有する燐酸アルミニウム組成物、それの製造方法およびそれの使用
JP2002520424A (ja) * 1998-07-09 2002-07-09 ダブリュー・アール・グレース・アンド・カンパニー−コーン インキ受理性コーティングに適した配合物
JP2006011175A (ja) * 2004-06-28 2006-01-12 Pentax Corp 反射防止膜を有する光学素子及びその製造方法
JP2006265091A (ja) * 2005-02-25 2006-10-05 Equos Research Co Ltd カーボンエアロゲル粉末の製造方法
JP2010521399A (ja) * 2007-03-16 2010-06-24 キャボット コーポレイション エーロゲル粒子及びそれらの製造方法
JP2017066251A (ja) * 2015-09-29 2017-04-06 日東電工株式会社 多孔体ゲル含有液の製造方法、多孔体ゲル含有液、高空隙層の製造方法、高空隙率多孔体の製造方法、および積層フィルムロールの製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06219717A (ja) * 1992-11-04 1994-08-09 Grace Gmbh 高い細孔容積と大きな孔直径を有する燐酸アルミニウム組成物、それの製造方法およびそれの使用
JP2002520424A (ja) * 1998-07-09 2002-07-09 ダブリュー・アール・グレース・アンド・カンパニー−コーン インキ受理性コーティングに適した配合物
JP2006011175A (ja) * 2004-06-28 2006-01-12 Pentax Corp 反射防止膜を有する光学素子及びその製造方法
JP2006265091A (ja) * 2005-02-25 2006-10-05 Equos Research Co Ltd カーボンエアロゲル粉末の製造方法
JP2010521399A (ja) * 2007-03-16 2010-06-24 キャボット コーポレイション エーロゲル粒子及びそれらの製造方法
JP2017066251A (ja) * 2015-09-29 2017-04-06 日東電工株式会社 多孔体ゲル含有液の製造方法、多孔体ゲル含有液、高空隙層の製造方法、高空隙率多孔体の製造方法、および積層フィルムロールの製造方法

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