[go: up one dir, main page]

WO2019070035A1 - Poudre composite d'aérogel et matériau hydrofuge - Google Patents

Poudre composite d'aérogel et matériau hydrofuge Download PDF

Info

Publication number
WO2019070035A1
WO2019070035A1 PCT/JP2018/037244 JP2018037244W WO2019070035A1 WO 2019070035 A1 WO2019070035 A1 WO 2019070035A1 JP 2018037244 W JP2018037244 W JP 2018037244W WO 2019070035 A1 WO2019070035 A1 WO 2019070035A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
airgel
water repellent
silica particles
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/037244
Other languages
English (en)
Japanese (ja)
Inventor
雄太 赤須
竜也 牧野
智彦 小竹
抗太 岩永
知里 吉川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of WO2019070035A1 publication Critical patent/WO2019070035A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present disclosure relates to an airgel composite powder and a water repellent.
  • water repellency is obtained by forming a film (hereinafter referred to as "water repellent film") on the surface of a substrate with a coating material excellent in water repellency.
  • the water repellent film generally means a film having a contact angle of water of 90 ° or more.
  • PTFE polytetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • the application site and substrate are limited.
  • Patent Documents 1 and 2 disclose that a water repellent film is formed using a fluoroalkylsilane.
  • Patent Documents 3 and 4 disclose that water repellency is imparted using a dispersion of fluorine-containing nanoparticles.
  • JP 2002-105661 A JP 2000-81214 A JP, 2016-44092, A Patent No. 5996056 gazette
  • the water-repellent film formed from fluoroalkylsilane does not have sufficient adhesion to the substrate, it is difficult to apply the fluoroalkylsilane to the substrate to form a water-repellent film excellent in flexibility.
  • it is possible to impart water repellency by using a powder having water repellency since dispersion in water is difficult, it is necessary to use an organic solvent, and the environmental load is large.
  • powders that can be dispersed in water generally have poor water repellency. Therefore, a water repellent material which has both water repellency and dispersibility in water and is excellent in adhesion and flexibility is required.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water repellent powder which has both water repellency and dispersibility in water and is excellent in adhesion and flexibility.
  • the present disclosure contains an airgel component and silica particles, and the airgel component has at least one polar group selected from the group consisting of an epoxy group, a mercapto group, an acryloyl group, a methacryloyl group and an amino group.
  • the airgel composite powder according to the present disclosure can be dispersed in water and has excellent adhesion, flexibility, and water repellency.
  • the airgel composite powder can have a three-dimensional network structure formed of an airgel component and silica particles, and pores. This makes it easier to further improve the flexibility and the water repellency.
  • the airgel composite powder is selected from the group consisting of silica particles, a silicon compound having a hydrolyzable functional group or a condensable functional group, and a hydrolysis product of a silicon compound having a hydrolyzable functional group. It may be a dry product of a wet gel which is a condensate of a sol containing at least one of Such airgel composite powder is likely to further improve the flexibility and water repellency.
  • the average primary particle size of the silica particles can be 1 to 500 nm.
  • the silica particles may be amorphous silica particles.
  • the amorphous silica particles may be at least one selected from the group consisting of fused silica particles, fumed silica particles and colloidal silica particles.
  • the airgel composite powder comprises, from the group consisting of silane particles, a polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and a hydrolysis product of a polysiloxane compound having a hydrolyzable functional group. It may be a dry product of a wet gel which is a condensate of a sol containing at least one selected.
  • the airgel component may have a structure represented by the general formula (1).
  • R 1 and R 2 each independently represent an alkyl group or an aryl group
  • R 3 and R 4 each independently represent an alkylene group.
  • the airgel component may have a ladder structure having a support portion and a bridging portion, and the bridging portion may have a structure represented by the following general formula (2).
  • R 5 and R 6 each independently represent an alkyl group or an aryl group, and b represents an integer of 1 to 50.
  • the airgel component may have a ladder-type structure represented by the following general formula (3).
  • R 5 , R 6 , R 7 and R 8 each independently represent an alkyl group or an aryl group
  • a and c each independently represent an integer of 1 to 3000
  • b is 1 to 50. Indicates an integer.
  • the average particle size D50 of the airgel composite powder can be 1 to 1000 ⁇ m. Thereby, the formability and adhesion of the water repellent film to the surface to be treated of the adherend are further improved.
  • the present disclosure also provides a water repellent material including the above-described airgel composite powder.
  • the present invention it is possible to provide an airgel composite powder excellent in water repellency and flexibility and a water repellent using the same. Since the airgel composite powder of the present invention can impart water repellency to the surface to be treated at low temperature, it can impart excellent water repellency even to adherends that do not have heat resistance. Moreover, this airgel composite powder is excellent in flexibility and adhesion to an adherend, and can maintain a water repellant function for a long time. Furthermore, since it is also dispersed in water, the environmental load can be reduced without using an organic solvent.
  • ⁇ Aerogel complex powder> dry gel obtained by supercritical drying method for wet gel is aerogel, dry gel obtained by drying under atmospheric pressure is xerogel, and dry gel obtained by lyophilization is cryogel
  • the resulting low density dried gel is referred to as "aerogel” regardless of these drying techniques of the wet gel. That is, in the present embodiment, the term “aerogel” means "gel composed of a microporous solid in which the dispersed phase is gas (a gel composed of a microporous solid in which the dispersed phase is gas)", which is an airgel in a broad sense. It is a thing.
  • the inside of the airgel has a network-like microstructure, and has a cluster structure in which airgel particles (particles constituting the airgel) of about 2 to 20 nm are bonded. Between the frameworks formed by the clusters, there are pores less than 100 nm. Thus, the airgel has a three-dimensionally fine porous structure.
  • the airgel in this embodiment is a silica airgel which has a silica as a main component, for example.
  • the silica aerogels include so-called organic-inorganic hybridised silica aerogels into which organic groups (such as methyl groups) or organic chains have been introduced.
  • the airgel composite powder (also referred to as powder (powdery) aerogel) according to the present embodiment has a cluster structure which is a feature of the above-mentioned airgel, and has a three-dimensionally fine porosity. It is a powder having a structure.
  • the airgel composite powder of the present embodiment includes at least one polar group selected from the group consisting of an epoxy group (for example, glycidoxy group), a mercapto group, an acryloyl group, a methacryloyl group and an amino group (hereinafter referred to as “specific Containing an airgel component having a polar group).
  • an epoxy group for example, glycidoxy group
  • a mercapto group an acryloyl group
  • methacryloyl group a methacryloyl group
  • an amino group hereinafter referred to as “specific Containing an airgel component having a polar group.
  • the airgel complex powder according to the present embodiment may be an airgel complex containing an airgel component and silica particles.
  • the airgel composite powder according to the present embodiment can be expressed as containing silica particles as a component constituting a three-dimensional network structure. It is.
  • the airgel composite powder according to the present embodiment is excellent in water repellency and flexibility as described later. In particular, it can be suitably used as a water repellent powder having excellent adhesion due to its excellent flexibility.
  • Such an airgel composite powder is obtained by the presence of silica particles in the airgel manufacturing environment.
  • the merit of the presence of the silica particles is not only that the water repellency, flexibility, etc.
  • the airgel component may be indeterminate form such as a film or the like, or may be particulate (aerogel particles).
  • the airgel component since the airgel component is in various forms and is present between the silica particles, it is presumed that the flexibility of the airgel skeleton is imparted.
  • an amorphous airgel component intervenes between the silica particles.
  • silica particles are coated with a film-like airgel component (silicone component) (aspect in which the airgel component incorporates silica particles), the airgel component serves as a binder, and silica particles
  • the embodiment of the combination of these embodiments the embodiment in which the silica particles arranged in a cluster form are coated with the airgel component, etc.
  • the three-dimensional network structure can be composed of the silica particles and the airgel component (silicone component), and the specific aspect (form) thereof is not particularly limited.
  • the airgel component may not be indeterminate form, but may be in the form of clear particles as shown in FIG. 1 and be complexed with the silica particles.
  • the present inventor infers that the production
  • the formation rate of the airgel component tends to vary.
  • the production rate of the airgel component tends to fluctuate also by changing the pH of the system.
  • the aspect (size, shape, chemical structure, etc. of the three-dimensional network structure) of the airgel composite powder can be controlled by adjusting the size, shape, number of silanol groups, pH of the system, etc. of the silica particles. . Therefore, it is possible to control the density, the porosity, and the like of the airgel, and to control the heat insulation property, the flexibility, the penetration resistance of the resin, and the like of the airgel.
  • the three-dimensional network structure of the airgel complex powder may be comprised from only one type of the various aspect mentioned above, and may be comprised from two or more types of aspects.
  • FIG. 1 is a view schematically showing the microstructure of an airgel composite powder according to an embodiment of the present disclosure.
  • the airgel complex 10 has a three-dimensional network structure formed by the airgel particles 1 constituting the airgel component being partially and randomly connected three-dimensionally via the silica particles 2, And a pore 3 surrounded by the skeleton.
  • the silica particle 2 intervenes between the airgel particle 1, and functions as a frame
  • the airgel complex powder may have a three-dimensional network structure formed by the silica particles being randomly connected three-dimensionally through the airgel particles.
  • the silica particles may also be coated with airgel particles.
  • grains (airgel component) are comprised from a silicon compound, it is guessed that the affinity to a silica particle is high. Therefore, in the present embodiment, it is considered that silica particles were successfully introduced into the three-dimensional network of the airgel. In this respect, the silanol groups of the silica particles are also considered to contribute to the affinity of the two.
  • the airgel particles 1 are considered to be in the form of secondary particles composed of a plurality of primary particles, and are generally spherical.
  • the average particle size (ie, secondary particle size) of the airgel particles 1 can be 2 nm to 50 ⁇ m, but may be 5 nm to 2 ⁇ m, or 10 nm to 200 nm.
  • the average particle diameter of the airgel particle 1 is 2 nm or more, an airgel composite powder excellent in flexibility is easily obtained, while when the average particle diameter is 50 ⁇ m or less, an airgel composite powder excellent in heat insulation is obtained. It will be easier.
  • the average particle diameter of the primary particles constituting the airgel particle 1 can be 0.1 nm to 5 ⁇ m from the viewpoint of easily forming a secondary particle having a low density porous structure, but 0.5 nm to It may be 200 nm or 1 nm to 20 nm.
  • the silica particles 2 can be used without particular limitation, and examples thereof include amorphous silica particles.
  • the amorphous silica particles include at least one selected from the group consisting of fused silica particles, fumed silica particles and colloidal silica particles. Among these, colloidal silica particles have high monodispersity, and easily suppress aggregation in the sol.
  • the silica particles 2 may be silica particles having a hollow structure, a porous structure or the like.
  • the shape of the silica particles 2 is not particularly limited, and examples thereof include spheres, bowls, and association types. Among these, use of spherical particles as the silica particles 2 makes it easy to suppress aggregation in the sol.
  • the average primary particle diameter of the silica particles 2 can be 1 to 500 nm, but may be 5 to 300 nm, or 20 to 100 nm. When the average primary particle diameter of the silica particles 2 is 1 nm or more, appropriate strength can be easily imparted to the airgel, and an airgel composite powder excellent in shrinkage resistance at the time of drying can be easily obtained. On the other hand, when the average primary particle diameter is 500 nm or less, an airgel composite powder excellent in water repellency can be easily obtained.
  • the airgel particles 1 (airgel component) and the silica particles 2 are bonded in the form of hydrogen bonding or chemical bonding.
  • a hydrogen bond or a chemical bond is formed by the silanol group or polar group of the airgel particle 1 (airgel component) and the silanol group of the silica particle 2. Therefore, it is considered that when the bonding mode is a chemical bond, it is easy to impart appropriate strength to the airgel. From this point of view, it is possible to use not only silica particles but also inorganic particles or organic particles having silanol groups on the particle surface as particles to be complexed with the airgel component.
  • the number of silanol groups per 1 g of the silica particles 2 can be 10 ⁇ 10 18 to 1000 ⁇ 10 18 pieces / g, but may be 50 ⁇ 10 18 to 800 ⁇ 10 18 pieces / g, or 100 It may be ⁇ 10 18 to 700 ⁇ 10 18 pieces / g.
  • the number of silanol groups per 1 g of the silica particle 2 is 10 ⁇ 10 18 pieces / g or more, it is possible to have better reactivity with the airgel particle 1 (airgel component), and an airgel composite excellent in shrinkage resistance It becomes easy to obtain body powder.
  • the number of silanol groups is 1000 ⁇ 10 18 pieces / g or less, sudden gelation at the time of sol preparation can be easily suppressed, and homogeneous airgel composite powder can be easily obtained.
  • the average particle diameter of the particles is an airgel composite using a scanning electron microscope (hereinafter abbreviated as “SEM”).
  • SEM scanning electron microscope
  • the particle size of airgel particles or individual silica particles can be obtained based on the diameter of the cross section.
  • the term "diameter” as used herein means the diameter when the cross section of the skeleton forming the three-dimensional network structure is regarded as a circle.
  • the diameter when the cross section is regarded as a circle is the diameter of the circle when the area of the cross section is replaced with a circle of the same area.
  • yen is calculated
  • the biaxial average primary particle diameter is calculated as follows from the result of observing 20 arbitrary particles by SEM. That is, for example, when colloidal silica particles having a solid content concentration of 5 to 40% by mass dispersed in water are taken as an example, a chip obtained by cutting a wafer with pattern wiring into 2 cm square is dipped for about 30 seconds in the dispersion liquid of colloidal silica particles. After that, the chip is rinsed with pure water for about 30 seconds and dried by nitrogen blow.
  • the chip is placed on a sample stage for SEM observation, an acceleration voltage of 10 kV is applied, silica particles are observed at a magnification of 100,000 times, and an image is photographed. Twenty silica particles are arbitrarily selected from the obtained image, and the average of the particle sizes of those particles is taken as the average particle size.
  • the selected silica particle is a shape as shown in FIG. 2, the rectangle (outside rectangle L) which circumscribeds the silica particle 2 and arrange
  • the biaxial average primary particle diameter is calculated with (X + Y) / 2 as the particle diameter of the particles.
  • the shape of the airgel complex powder according to the present embodiment is not particularly limited, and may be various shapes. Since the airgel composite powder in the present embodiment is pulverized to be powdered as described later, the powder usually has an irregular shape with irregularities on the surface. Of course, spherical powder and the like may be used. In addition, it may be in the form of panel, flake or fiber. The powder shape can be obtained by directly observing the airgel composite powder using an SEM.
  • the average particle diameter D50 of the airgel complex powder according to the present embodiment can be 1 to 1000 ⁇ m, but may be 3 to 700 ⁇ m, or 5 to 500 ⁇ m.
  • the average particle diameter D50 of the airgel complex powder is 1 ⁇ m or more, the airgel complex powder having excellent dispersibility and handling property can be easily obtained.
  • the average particle diameter D50 is 1000 ⁇ m or less, an airgel composite powder excellent in dispersibility is easily obtained.
  • the average particle size of the powder can be appropriately adjusted according to the method of grinding and conditions of grinding, the manner of sieving or classification.
  • the average particle size D50 of the powder can be measured by a laser diffraction / scattering method.
  • airgel complex powder is added to a solvent (ethanol) at a concentration of 0.05 to 5% by mass, and the powder is dispersed by vibrating for 15 to 30 minutes with a 50 W ultrasonic homogenizer. Thereafter, about 10 mL of the dispersion is injected into a laser diffraction / scattering particle size distribution measuring apparatus, and the particle size is measured at 25 ° C. with a refractive index of 1.3 and an absorption of 0. Then, the particle diameter at an integrated value of 50% (volume basis) in this particle diameter distribution is taken as an average particle diameter D50.
  • Microtrac MT3000 product name, manufactured by Nikkiso Co., Ltd.
  • the size of the pores 3, that is, the average pore diameter can be 5 to 1000 nm, but may be 25 to 500 nm.
  • the average pore diameter is 5 nm or more, the airgel composite powder having excellent flexibility is easily obtained, and when the average pore diameter is 1000 nm or less, the airgel composite powder having excellent water repellency is easily obtained.
  • the average pore size, density and porosity of the three-dimensional network-like continuous pores (through pores) of the airgel composite powder can be measured by mercury porosimetry according to DIN 66133.
  • Autopore IV9520 manufactured by Shimadzu Corporation, product name
  • Shimadzu Corporation product name
  • the compressive elastic modulus at 25 ° C. of the airgel composite powder of the present embodiment can be 2.0 MPa or less, and may be 1.5 MPa or less, or 1.3 MPa or less, 1.0 MPa It may be the following.
  • the lower limit value of the compression elastic modulus is not particularly limited, but may be, for example, 0.05 MPa.
  • the compressive elastic modulus can be measured using a micro compression tester "MCT-510" (product name, manufactured by Shimadzu Corporation).
  • the airgel composite powder of the present embodiment can contain a polysiloxane having a main chain containing a siloxane bond (Si-O-Si).
  • the airgel can have the following M units, D units, T units or Q units as structural units.
  • R represents an atom (such as a hydrogen atom) or an atomic group (such as an alkyl group) bonded to a silicon atom.
  • the M unit is a unit consisting of a monovalent group in which a silicon atom is bonded to one oxygen atom.
  • the D unit is a unit consisting of a divalent group in which a silicon atom is bonded to two oxygen atoms.
  • the T unit is a unit consisting of a trivalent group in which a silicon atom is bonded to three oxygen atoms.
  • the Q unit is a unit consisting of a tetravalent group in which a silicon atom is bonded to four oxygen atoms. Information on the content of these units can be obtained by Si-NMR.
  • Examples of the airgel component in the airgel complex powder according to the present embodiment include the following modes. By adopting these aspects, it becomes easy to control the thermal insulation and flexibility of the airgel composite powder to a desired level.
  • the airgel component of the airgel complex powder according to the present embodiment can have a structure represented by the following general formula (1).
  • the airgel component of the airgel complex powder according to the present embodiment can have a structure represented by the following general formula (1a) as a structure including the structure represented by the formula (1).
  • R 1 and R 2 each independently represent an alkyl group or an aryl group
  • R 3 and R 4 each independently represent an alkylene group.
  • an aryl group a phenyl group, a substituted phenyl group, etc. are mentioned.
  • a substituent of a substituted phenyl group an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, a cyano group etc. are mentioned.
  • p represents an integer of 1 to 50.
  • two or more R 1 s may be the same as or different from each other, and similarly, two or more R 2 s may be the same as or different from each other.
  • two R 3 s may be the same or different, and similarly, two R 4 s may be the same or different.
  • R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms, a phenyl group or the like. A methyl group etc. are mentioned.
  • R 3 and R 4 each independently represent an alkylene group having 1 to 6 carbon atoms, and the alkylene group is, for example, an ethylene group or a propylene group. Can be mentioned.
  • p may be 2 to 30, and may be 5 to 20.
  • the airgel component of the airgel complex powder according to the present embodiment can have a ladder structure having a support portion and a crosslinking portion, and the crosslinking portion can have a structure represented by the following general formula (2) .
  • Heat resistance and mechanical strength can be improved by introducing such a ladder-type structure as the airgel component into the skeleton of the airgel complex powder.
  • the term “ladder type structure” refers to one having two struts (struts) and bridges connecting the struts (so-called “ladder”). It is.
  • the skeleton of the airgel may have a ladder structure, but the airgel component may partially have a ladder structure.
  • R 5 and R 6 each independently represent an alkyl group or an aryl group, and b represents an integer of 1 to 50.
  • a aryl group a phenyl group and a substituted phenyl group are mentioned, for example.
  • a substituent of a substituted phenyl group an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group are mentioned, for example.
  • b is an integer of 2 or more
  • two or more R 5 s may be the same as or different from each other, and similarly, two or more R 6 s may be the same as each other May also be different.
  • silsesquioxane is a polysiloxane having a compositional formula: (RSiO 1.5 ) n and can have various skeleton structures such as a cage type, a ladder type, and a random type.
  • the structure of the cross-linked portion of the airgel component is -O- (having the above-mentioned T unit as a structural unit)
  • the structure of the crosslinked portion of the airgel component may be a structure (polysiloxane structure) represented by the above general formula (2).
  • the airgel component in the airgel complex powder of the present embodiment may have a structure derived from silsesquioxane in addition to the structure represented by the general formula (2).
  • R represents a hydroxy group, an alkyl group or an aryl group.
  • the ladder type structure It may have a ladder type structure represented by 3).
  • R 5 , R 6 , R 7 and R 8 each independently represent an alkyl group or an aryl group
  • a and c each independently represent an integer of 1 to 3000
  • b is 1 to 50.
  • an aryl group a phenyl group and a substituted phenyl group are mentioned, for example.
  • a substituent of a substituted phenyl group an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group are mentioned, for example.
  • R 5 , R 6 , R 7 and R 8 (wherein R 7 and R 8 are only in the formula (3)) And each independently represent an alkyl group having 1 to 6 carbon atoms, a phenyl group or the like, and examples of the alkyl group include a methyl group.
  • a and c can be independently 6 to 2000, but may be 10 to 1000.
  • b can be 2 to 30, but may be 5 to 20.
  • the airgel composite powder according to the present embodiment comprises silica particles, a silicon compound having a hydrolyzable functional group or a condensable functional group, and a hydrolysis product of a silicon compound having a hydrolyzable functional group.
  • a dried product of a wet gel which is a condensation product of a sol containing at least one member selected from the group consisting of (a dried product of a wet gel formed from the sol and obtained by drying the dry product of a wet gel derived from a sol) It may be.
  • the airgel composite powder described above may also be obtained by drying the wet gel produced from the sol containing the silica particles and the silicon compound and the like.
  • silicon compounds (silicon compounds) other than the below-mentioned polysiloxane compound can be used. That is, the sol is a group consisting of a silicon compound having hydrolyzable functional groups or condensable functional groups (excluding polysiloxane compounds), and a hydrolysis product of a silicon compound having hydrolyzable functional groups. It may contain at least one compound selected from the group below (hereinafter sometimes referred to as “silicon compound group”). The number of silicon in the molecule in the silicon compound can be 1 or 2.
  • the silicon compound having a hydrolyzable functional group is not particularly limited, and examples thereof include alkyl silicon alkoxides.
  • the alkyl silicon alkoxide can have three or less hydrolyzable functional groups from the viewpoint of improving water resistance.
  • Examples of the alkylsilicon alkoxide include monoalkyltrialkoxysilanes, monoalkyldialkoxysilanes, dialkyldialkoxysilanes, monoalkylmonoalkoxysilanes, dialkylmonoalkoxysilanes, trialkylmonoalkoxysilanes, etc.
  • methyl Examples include trimethoxysilane, methyldimethoxysilane, dimethyldimethoxysilane and ethyltrimethoxysilane.
  • alkoxy groups such as a methoxy group and an ethoxy group, etc. are mentioned.
  • the silicon compound having a condensable functional group is not particularly limited.
  • silanetetraol methylsilanetriol, dimethylsilanediol, phenylsilanetriol, phenylmethylsilanediol, diphenylsilanediol, n-propylsilanetriol, Hexylsilanetriol, octylsilanetriol, decylsilanetriol and trifluoropropylsilanetriol.
  • a silicon compound having a hydrolyzable functional group or a condensable functional group is a polar group (hydrolyzable functional group and a condensable functional group) different from the hydrolyzable functional group and the condensable functional group.
  • Functional groups may be further included.
  • a polar group an epoxy group, a mercapto group, a vinyl group, an acryloyl group, a methacryloyl group, and an amino group are mentioned, for example.
  • the epoxy group may be contained in an epoxy group-containing group such as a glycidoxy group. From the viewpoint of dispersibility in water, as a polar group, an epoxy group, a mercapto group, a glycidoxy group, an acryloyl group, a methacryloyl group and an amino group are preferable.
  • silicon compounds having a condensable functional group and having a polar group vinylsilanetriol, 3-glycidoxypropylsilanetriol, 3-glycidoxypropylmethylsilanediol, 3-methacryloxypropylsilanetriol, 3 -Methacryloxypropylmethylsilanediol, 3-acryloxypropylsilanetriol, 3-mercaptopropylsilanetriol, 3-mercaptopropylmethylsilanediol, N-phenyl-3-aminopropylsilanetriol, N-2- (aminoethyl) -3-aminopropylmethylsilanediol and the like can also be used.
  • bistrimethoxysilylmethane, bistrimethoxysilylethane, bistrimethoxysilylhexane, ethyltrimethoxysilane, vinyltrimethoxysilane, etc. which are silicon compounds having three or less hydrolyzable functional groups at the molecular end, can also be used.
  • Silicon compounds having hydrolyzable functional groups or condensable functional groups (excluding polysiloxane compounds) and hydrolysis products of silicon compounds having hydrolyzable functional groups may be used alone or in combination of two or more. You may mix and use.
  • the silicon compound can include a polysiloxane compound having a hydrolyzable functional group or a condensable functional group. That is, the sol containing the above silicon compound is composed of a hydrolysis product of a polysiloxane compound having a hydrolyzable functional group or a condensation functional group, and a polysiloxane compound having a hydrolyzable functional group. It may be a sol containing at least one selected from the group (hereinafter sometimes referred to as “polysiloxane compound group”).
  • the functional groups in the polysiloxane compound and the like are not particularly limited, but can be groups that react with each other or react with other functional groups.
  • a hydrolyzable functional group an alkoxy group is mentioned, for example.
  • the condensation functional group include a hydroxyl group, a silanol group, a carboxyl group and a phenolic hydroxyl group.
  • the hydroxyl group may be contained in a hydroxyl group-containing group such as a hydroxyalkyl group.
  • the polysiloxane compound having a hydrolyzable functional group or a condensable functional group is different from the hydrolyzable functional group and the condensable functional group in the aforementioned polar group (hydrolyzable functional group and condensable) Functional groups which do not correspond to the functional groups of You may use the polysiloxane compound which has these functional groups and polar groups individually or in mixture of 2 or more types.
  • these functional groups and polar groups for example, as a group improving the flexibility of the airgel composite powder, alkoxy group, silanol group, hydroxyalkyl group and the like can be mentioned, and among these, alkoxy group and hydroxyalkyl group Can further improve the compatibility of the sol.
  • the carbon number of the alkoxy group and the hydroxyalkyl group can be 1 to 6, but from the viewpoint of further improving the flexibility of the airgel composite powder, 2 to 4 It may be
  • the compound which has a structure represented by the following general formula (A) is mentioned, for example.
  • Introducing the structures represented by the general formula (1) and the formula (1a) into the skeleton of the airgel composite powder by using a polysiloxane compound having a structure represented by the following general formula (A) Can.
  • R 1a represents a hydroxyalkyl group
  • R 2a represents an alkylene group
  • R 3a and R 4a each independently represent an alkyl group or an aryl group
  • n represents an integer of 1 to 50.
  • an aryl group a phenyl group and a substituted phenyl group are mentioned, for example.
  • a substituent of a substituted phenyl group an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group are mentioned, for example.
  • two R 1a 's may be the same as or different from each other, and similarly, two R 2a' s may be the same as or different from each other.
  • two or more R 3a s may be the same as or different from each other.
  • two or more R 4a s may be the same as or different from each other.
  • R 1a includes a hydroxyalkyl group having 1 to 6 carbon atoms, and the like, and examples of the hydroxyalkyl group include a hydroxyethyl group, a hydroxypropyl group and the like.
  • examples of R 2a include an alkylene group having 1 to 6 carbon atoms, and examples of the alkylene group include an ethylene group and a propylene group.
  • R 3a and R 4a each independently represent an alkyl group having 1 to 6 carbon atoms, a phenyl group or the like, and examples of the alkyl group include a methyl group.
  • n can be 2 to 30, but may be 5 to 20.
  • a commercial item can be used as a polysiloxane compound which has a structure represented by the said General formula (A), Compounds, such as X-22-160AS, KF-6001, KF-6002, KF-6003 (all are mentioned And Shin-Etsu Chemical Co., Ltd., XF42-B0970, Fluid OFOH 702-4%, etc. (all are manufactured by Momentive, Inc.) and the like.
  • polysiloxane compound which has an alkoxy group what has a structure represented by the following general formula (B) is mentioned, for example.
  • a ladder type structure having a crosslinked part represented by the above general formula (2) is introduced into the skeleton of the airgel composite powder can do.
  • R 1b represents an alkyl group, an alkoxy group or an aryl group
  • R 2b and R 3b each independently represent an alkoxy group
  • R 4b and R 5b each independently represent an alkyl group or an aryl group.
  • m represent an integer of 1 to 50.
  • an aryl group a phenyl group and a substituted phenyl group are mentioned, for example.
  • a substituent of a substituted phenyl group an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group are mentioned, for example.
  • two R 1b 's may be the same as or different from each other, and two R 2b' s may be the same as or different from one another, 3b may be the same or different.
  • m is an integer of 2 or more
  • two or more R 4b may be the same or different
  • two or more R 5b are also the same May also be different.
  • R 1b an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the like can be mentioned, and as the alkyl group or alkoxy group, A methyl group, a methoxy group, an ethoxy group etc. are mentioned.
  • examples of R 2b and R 3b each independently include an alkoxy group having 1 to 6 carbon atoms, and the alkoxy group includes a methoxy group and an ethoxy group.
  • examples of R 4b and R 5b each independently include an alkyl group having 1 to 6 carbon atoms, a phenyl group and the like, and examples of the alkyl group include a methyl group and the like.
  • m can be 2 to 30, but may be 5 to 20.
  • the polysiloxane compound having a structure represented by the above general formula (B) can be obtained by appropriately referring to the production method reported in, for example, JP-A-2000-26609, JP-A-2012-233110, etc. Can.
  • the polysiloxane compound having the alkoxy group may be present as a hydrolysis product in the sol, and the polysiloxane compound having the alkoxy group and the hydrolysis product thereof are mixed It may be done. Further, in the polysiloxane compound having an alkoxy group, all of the alkoxy groups in the molecule may be hydrolyzed or may be partially hydrolyzed.
  • hydrolyzable functional groups or the polysiloxane compound having a condensable functional group, and the hydrolysis product of the hydrolyzable functional group-containing polysiloxane compound may be used alone or in combination of two or more. You may use.
  • Content of silicon compounds contained in the above sol (content of silicon compound having hydrolyzable functional group or condensable functional group, and hydrolysis product of silicon compound having hydrolyzable functional group
  • the total sum of the contents can be 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of the sol, but may be 10 to 30 parts by mass.
  • the amount is 5 parts by mass or more, good reactivity can be easily obtained, and when the amount is 50 parts by mass or less, good compatibility can be easily obtained.
  • the content of the silicon compound group and the content of the polysiloxane compound group (the content of the polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and
  • the total sum of the content of the hydrolysis products of the hydrolyzable functional group-containing polysiloxane compound can be 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of the sol, but It may be 30 parts by mass.
  • the ratio of the content of the silicon compound group to the content of the polysiloxane compound group can be 0.5: 1 to 4: 1, but may be 1: 1 to 2: 1. .
  • the ratio of the content of these compounds can be 0.5: 1 or more, good compatibility can be further easily obtained, and by setting the ratio to 4: 1 or less, gel contraction can be further easily suppressed.
  • the content of the silica particles contained in the sol can be 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of sol, but may be 4 to 15 parts by mass.
  • the content of the silica particles By setting the content of the silica particles to 1 part by mass or more, it becomes easy to impart appropriate strength to the airgel, and it becomes easy to obtain an airgel composite powder excellent in shrinkage resistance during drying, and the content is 20 parts by mass or less By doing this, it becomes easy to suppress the solid heat conduction of the silica particles, and it becomes easy to obtain the airgel composite powder which is excellent in heat insulation.
  • the airgel component of the airgel complex powder according to the present embodiment can have a structure represented by the following general formula (4).
  • the airgel composite powder according to the present embodiment may contain silica particles and may have a structure represented by the following general formula (4) as an airgel component.
  • R 9 represents an alkyl group.
  • the alkyl group an alkyl group having 1 to 6 carbon atoms and the like can be mentioned, and as the alkyl group, a methyl group and the like can be mentioned.
  • the airgel component of the airgel complex powder according to the present embodiment can have a structure represented by the following general formula (5).
  • the airgel composite powder according to the present embodiment may contain silica particles and may have a structure represented by the following general formula (5) as an airgel component.
  • R 10 and R 11 each independently represent an alkyl group.
  • the alkyl group an alkyl group having 1 to 6 carbon atoms and the like can be mentioned, and as the alkyl group, a methyl group and the like can be mentioned.
  • the airgel component of the airgel complex powder according to the present embodiment can have a structure represented by the following general formula (6).
  • the airgel composite powder of the present embodiment may contain silica particles and may have a structure represented by the following general formula (6) as an airgel component.
  • R 12 represents an alkylene group.
  • examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms, and examples of the alkylene group include ethylene group and hexylene group.
  • the airgel complex powder according to the present embodiment is obtained by the sol forming step, the wet gel forming step of gelling the sol obtained in the sol forming step, and then maturing to obtain a wet gel, and the wet gel forming step. Washing and solvent replacement steps of the wet gel obtained (if necessary), a drying step of drying the washed and solvent substituted wet gel, and block grinding of the airgel composite block obtained by drying It can manufacture by the manufacturing method mainly equipped with a process.
  • the method mainly includes a sol forming step, the wet gel forming step, a wet gel grinding step of grinding the wet gel obtained in the wet gel forming step, the washing and solvent substitution steps, and the drying step. It may be manufactured by a method.
  • the obtained airgel composite powder can be further aligned in size by sieving, classification and the like.
  • "sol” is a state before the gelation reaction occurs, and in the present embodiment, the silicon compound group, and optionally, the polysiloxane compound group and the silica particles are dissolved or dispersed in a solvent.
  • wet gel refers to a gel solid in a wet state having no flowability while containing a liquid medium.
  • the sol formation step is a step of mixing the above-mentioned silicon compound, optionally a polysiloxane compound, and a silica particle or a solvent containing a silica particle, and hydrolyzing to form a sol.
  • an acid catalyst may be further added to the solvent to accelerate the hydrolysis reaction.
  • a surfactant, a thermally hydrolysable compound and the like can also be added to the solvent.
  • components such as carbon graphite, an aluminum compound, a magnesium compound, a silver compound, and a titanium compound may be added to the solvent.
  • the solvent for example, water or a mixed solution of water and alcohols can be used.
  • the alcohol include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, t-butanol and the like.
  • the alcohol having a low surface tension and a low boiling point methanol, ethanol, 2-propanol and the like can be mentioned in that the interfacial tension with the gel wall is reduced. You may use these individually or in mixture of 2 or more types.
  • the amount of the alcohols can be 4 to 8 moles with respect to 1 mole in total of the silicon compound group and the polysiloxane compound group, but it is 4 to 6.5 Or may be 4.5 to 6 moles.
  • the amount of the alcohol 4 mol or more it becomes easier to obtain good compatibility, and by making it 8 mol or less, it becomes easier to suppress the shrinkage of the gel.
  • inorganic acids such as hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, bromic acid, chloric acid, chlorous acid, hypochlorous acid, etc .
  • Acidic phosphates such as aluminum, acidic magnesium phosphate, acidic zinc phosphate, etc .
  • Organic carboxylic acids such as acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid, azelaic acid Etc.
  • organic carboxylic acids are mentioned as an acid catalyst which improves the water resistance of the airgel complex powder obtained more.
  • the organic carboxylic acids include acetic acid, but formic acid, propionic acid, oxalic acid, malonic acid and the like may be used. You may use these individually or in mixture of 2 or more types.
  • the hydrolysis reaction of the silicon compound group and the polysiloxane compound group can be promoted to obtain a sol in a shorter time.
  • the addition amount of the acid catalyst can be 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total of the silicon compound group and the polysiloxane compound group.
  • nonionic surfactants nonionic surfactants, ionic surfactants and the like can be used. You may use these individually or in mixture of 2 or more types.
  • nonionic surfactant for example, a compound containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group, a compound containing a hydrophilic part such as polyoxypropylene and the like can be used.
  • a compound containing a hydrophilic moiety such as polyoxyethylene and a hydrophobic moiety mainly composed of an alkyl group include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether and the like.
  • the compound containing a hydrophilic portion such as polyoxypropylene include polyoxypropylene alkyl ether and block copolymers of polyoxyethylene and polyoxypropylene.
  • Examples of the ionic surfactant include cationic surfactants, anionic surfactants and amphoteric surfactants.
  • Examples of the cationic surfactant include cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and the like, and examples of the anionic surfactant include sodium dodecyl sulfonate and the like.
  • an amphoteric surfactant an amino acid surfactant, a betaine surfactant, an amine oxide surfactant, etc. are mentioned.
  • Examples of amino acid surfactants include, for example, acyl glutamic acid.
  • Examples of betaine surfactants include lauryl dimethylaminoacetic acid betaine and stearyl dimethylaminoacetic acid betaine.
  • Examples of amine oxide surfactants include lauryldimethylamine oxide.
  • surfactants have the function of reducing the difference in chemical affinity between the solvent in the reaction system and the growing siloxane polymer and suppressing the phase separation in the wet gel formation step described later. It is believed that.
  • the amount of surfactant added depends on the type of surfactant or the type and amount of silicon compound group and polysiloxane compound group.
  • the total amount of silicon compound group and polysiloxane compound group is 100 parts by mass.
  • it can be 1 to 100 parts by mass.
  • the addition amount may be 5 to 60 parts by mass.
  • thermohydrolyzable compound is considered to generate a base catalyst by thermal hydrolysis to make the reaction solution basic and to promote the sol-gel reaction in the wet gel formation step described later. Therefore, the thermohydrolyzable compound is not particularly limited as long as it is a compound that can make the reaction solution basic after hydrolysis, and urea; formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N And acid amides such as methylacetamide and N, N-dimethylacetamide; and cyclic nitrogen compounds such as hexamethylenetetramine. Among these, urea is particularly easy to obtain the above promoting effect.
  • the addition amount of the thermally hydrolysable compound is not particularly limited as long as it is an amount capable of sufficiently promoting the sol-gel reaction in the wet gel formation step described later.
  • the addition amount thereof can be 1 to 200 parts by mass with respect to 100 parts by mass in total of the silicon compound group and the polysiloxane compound group.
  • the addition amount may be 2 to 150 parts by mass.
  • the hydrolysis in the sol formation step depends on the type and amount of silicon compound, polysiloxane compound, silica particles, acid catalyst, surfactant, etc. in the mixed solution, for example, under a temperature environment of 20 to 60 ° C. It may be performed for 10 minutes to 24 hours, or may be performed for 5 minutes to 8 hours in a temperature environment of 50 to 60 ° C.
  • the hydrolyzable functional groups in the silicon compound and the polysiloxane compound are sufficiently hydrolyzed, and the hydrolysis product of the silicon compound and the hydrolysis product of the polysiloxane compound can be obtained more reliably.
  • the temperature environment of the sol formation step may be adjusted to a temperature at which the hydrolysis of the thermally hydrolysable compound is suppressed to suppress the gelation of the sol. .
  • the temperature at this time may be any temperature that can suppress the hydrolysis of the thermally hydrolysable compound.
  • the temperature environment of the sol formation step can be 0 to 40 ° C., but may be 10 to 30 ° C.
  • the wet gel formation step is a step of gelling the sol obtained in the sol formation step and then ripening to obtain a wet gel.
  • a base catalyst can be used to promote gelation.
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide
  • alkali carbonates such as sodium carbonate and potassium carbonate
  • alkali carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate Hydrogen salts
  • Ammonium compounds such as ammonium hydroxide, ammonium fluoride, ammonium chloride and ammonium bromide
  • Basic sodium phosphates such as sodium metaphosphate, sodium pyrophosphate and sodium polyphosphate
  • ammonium hydroxide (ammonia water) is high in volatility and less likely to remain in the airgel composite powder after drying, so that the water resistance is less likely to be impaired, and further, it is excellent in economic point.
  • the dehydration condensation reaction or the dealcoholization condensation reaction of the silicon compound, the polysiloxane compound and the silica particles in the sol can be promoted, and the gelation of the sol can be performed in a shorter time. Also, this makes it possible to obtain a wet gel with higher strength (rigidity).
  • ammonia has high volatility and is unlikely to remain in the airgel complex powder, and therefore, by using ammonia as a base catalyst, an airgel complex powder having more excellent water resistance can be obtained.
  • the addition amount of the base catalyst can be 0.5 to 5 parts by mass with respect to 100 parts by mass in total of the silicon compound group and the polysiloxane compound group, but may be 1 to 4 parts by mass. By setting it as 0.5 mass part or more, gelation can be performed in a short time, and the fall of water resistance can be suppressed more by setting it as 5 mass parts or less.
  • the base catalyst is not always necessary, and 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2
  • a silane compound or the like in which the aqueous solution such as-(aminoethyl) -3-aminopropylmethyldimethoxysilane exhibits basicity is used, a wet gel can also be produced without using a base catalyst.
  • the gelation of the sol in the wet gel formation step may be performed in a closed vessel so that the solvent and the base catalyst do not evaporate.
  • the gelling temperature may be 30-90 ° C., but may be 40-80 ° C.
  • the gelation temperature may be set to 30 ° C. or more, gelation can be performed in a shorter time, and a wet gel with higher strength (rigidity) can be obtained.
  • the gelation temperature to 90 ° C. or less, volatilization of the solvent (particularly, alcohols) can be easily suppressed, and therefore, gelation can be performed while suppressing volume contraction.
  • Aging in the wet gel formation step may be performed in a closed vessel so that the solvent and the base catalyst do not evaporate. Aging strengthens the bonding of the components constituting the wet gel, and as a result, it is possible to obtain a wet gel having a high strength (rigidity) sufficient to suppress shrinkage upon drying.
  • the ripening temperature may be 30 to 90 ° C., but may be 40 to 80 ° C. By setting the aging temperature to 30 ° C. or higher, a wet gel with higher strength (rigidity) can be obtained, and by setting the aging temperature to 90 ° C. or lower, volatilization of the solvent (particularly alcohols) can be easily suppressed. Therefore, it can be gelled while suppressing volume contraction.
  • the gelation of the sol and the subsequent aging may be performed in a series of continuous operations.
  • the gelation time and the ripening time differ depending on the gelation temperature and the ripening temperature, in the present embodiment, since the sol contains silica particles, especially the gelation time as compared with the conventional airgel manufacturing method. Can be shortened. The reason is presumed to be that the silicon compound group in the sol, the silanol group or the reactive group possessed by the polysiloxane compound group form a hydrogen bond or a chemical bond with the silanol group of the silica particle.
  • the gelling time may be 10 to 120 minutes, but may be 20 to 90 minutes.
  • the total time of the gelation time and the aging time can be 4 to 480 hours as the whole of the gelation and the aging process, but it may be 6 to 120 hours.
  • the total of the gelation time and the ripening time can be 4 hours or more, a wet gel with higher strength (rigidity) can be obtained, and by making it 480 hours or less, the effect of ripening can be more easily maintained.
  • the gelling temperature and the aging temperature are increased within the above range, or the total time of the gelling time and the aging time is long within the above range You may In addition, in order to increase the density of the obtained airgel composite powder and to reduce the average pore diameter, the gelling temperature and the aging temperature are lowered within the above range, or the total time of the gelling time and the aging time is the above range You may shorten it within.
  • the wet gel obtained in the wet gel formation process is ground.
  • the grinding can be carried out, for example, by placing the wet gel in a Henshall-type mixer or performing a wet gel formation step in the mixer and operating the mixer under appropriate conditions (rotation speed and time). Also, more simply, the wet gel is placed in a sealable container, or the wet gel formation step is performed in the sealable container, and shaking is performed using a shaking device such as a shaker for a suitable period of time. Can. If necessary, the particle size of the wet gel can also be adjusted using a jet mill, a roller mill, a bead mill or the like.
  • washing and solvent substitution steps are suitable for the step of washing the wet gel obtained by the wet gel formation step or the wet gel grinding step (washing step) and the washing solution in the wet gel for drying conditions (drying step described later) It is a process which has the process (solvent substitution process) of substituting with the said solvent.
  • the washing and solvent replacement steps can be carried out without washing the wet gel but with only the solvent replacement step, impurities such as unreacted substances and by-products in the wet gel can be reduced.
  • the wet gel may be washed from the viewpoint of enabling the production of highly pure airgel composite powder.
  • the solvent replacement step after the washing step is not necessarily essential as described later.
  • the wet gel obtained by the wet gel formation step or the wet gel grinding step is washed.
  • the washing can be repeated, for example, using water or an organic solvent. At this time, the washing efficiency can be improved by heating.
  • organic solvent methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, acetonitrile, hexane, toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran, methylene chloride
  • organic solvents such as N, N-dimethylformamide, dimethylsulfoxide, acetic acid, formic acid and the like can be used.
  • the organic solvents may be used alone or in combination of two or more.
  • examples of the organic solvent used in the washing step include hydrophilic organic solvents having high mutual solubility in both water and a solvent having low surface tension.
  • the hydrophilic organic solvent used in the washing step can play a role of pre-substitution for the solvent substitution step.
  • examples of the hydrophilic organic solvent include methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone and the like. Methanol, ethanol, methyl ethyl ketone and the like are excellent in economical point.
  • the amount of water or organic solvent used in the washing step may be such that the solvent in the wet gel is sufficiently replaced to be washable.
  • the amount can be 3 to 10 times the volume of the wet gel.
  • the washing can be repeated until the water content in the wet gel after washing becomes 10% by mass or less with respect to the mass of silica.
  • the temperature environment in the washing step can be set to a temperature equal to or lower than the boiling point of the solvent used for washing.
  • heating can be performed at about 30 to 60.degree.
  • the solvent of the washed wet gel is replaced with a predetermined replacement solvent in order to suppress shrinkage in the drying step described later.
  • the substitution efficiency can be improved by heating.
  • Specific examples of the substitution solvent include, in the drying step, a solvent having a low surface tension described later when drying under atmospheric pressure at a temperature less than the critical point of the solvent used for drying.
  • examples of the substitution solvent include ethanol, methanol, 2-propanol, dichlorodifluoromethane, carbon dioxide and the like, or solvents in which two or more of these are mixed.
  • solvents having a surface tension of 30 mN / m or less at 20 ° C. As a low surface tension solvent, solvents having a surface tension of 30 mN / m or less at 20 ° C. can be mentioned.
  • the surface tension may be 25 mN / m or less, or 20 mN / m or less.
  • low surface tension solvents examples include pentane (15.5), hexane (18.4), heptane (20.2), octane (21.7), 2-methylpentane (17.4), 3- Aliphatic hydrocarbons such as methyl pentane (18.1), 2-methyl hexane (19.3), cyclopentane (22.6), cyclohexane (25.2), 1-pentene (16.0); benzene Aromatic hydrocarbons such as (28.9), toluene (28.5), m-xylene (28.7), p-xylene (28.3); dichloromethane (27.9), chloroform (27.2) Halogenated hydrocarbons such as carbon tetrachloride (26.9), 1-chloropropane (21.8), 2-chloropropane (18.1), etc .; ethyl ether (17.1), propyl ether (20.5) ), Isop Ethers such as pill ether (17.7), buty
  • aliphatic hydrocarbons (hexane, heptane, etc.) have low surface tension and are excellent in working environment.
  • a hydrophilic organic solvent such as acetone, methyl ethyl ketone, 1,2-dimethoxyethane, etc.
  • a solvent having a boiling point of 100 ° C. or less at normal pressure may be used at the point of easy drying in the drying step described later.
  • the above solvents may be used alone or in combination of two or more.
  • the amount of solvent used in the solvent replacement step can be an amount that can sufficiently replace the solvent in the wet gel after washing.
  • the amount can be 3 to 10 times the volume of the wet gel.
  • the temperature environment in the solvent replacement step can be a temperature equal to or lower than the boiling point of the solvent used for the replacement, and, for example, in the case of using heptane, heating can be about 30 to 60 ° C.
  • the solvent substitution step is not necessarily essential as described above.
  • the presumed mechanism is as follows. That is, conventionally, the solvent of the wet gel has been replaced with a predetermined solvent for substitution (solvent of low surface tension) in order to suppress shrinkage in the drying step, but in the present embodiment, the silica particles have a three-dimensional network shape By acting as a scaffold support, the scaffold is supported, and the shrinkage of the gel in the drying step is suppressed. Therefore, it is considered that the gel can be directly subjected to the drying step without replacing the solvent used for the washing.
  • simplification of the drying process from the washing and solvent replacement process is possible.
  • this embodiment does not exclude at all from performing the solvent replacement step.
  • the drying method is not particularly limited, and known atmospheric pressure drying, supercritical drying or lyophilization can be used. Among these, atmospheric pressure drying or supercritical drying can be used from the viewpoint of easily producing a low density airgel composite block or powder. In addition, normal pressure drying can be used from the viewpoint of low cost production. In the present embodiment, normal pressure means 0.1 MPa (atmospheric pressure).
  • An airgel complex block or powder can be obtained by drying the washed and solvent-substituted wet gel at atmospheric pressure at a temperature below the critical point of the solvent used for drying.
  • the drying temperature varies depending on the type of the solvent which has been substituted (or the solvent used for washing if solvent substitution is not performed), particularly when drying at high temperature accelerates the evaporation rate of the solvent and causes the gel to greatly crack.
  • the temperature can be set to 20 to 150 ° C. in view of the following.
  • the drying temperature may be 60 to 120 ° C.
  • the drying time may vary depending on the wet gel volume and the drying temperature, but may be 4 to 120 hours. In the present embodiment, it is also included in normal-pressure drying to accelerate drying by applying a pressure less than the critical point within a range that does not impair productivity.
  • the airgel composite block or powder can also be obtained by supercritical drying of the washed and solvent-substituted wet gel (if necessary).
  • Supercritical drying can be performed by a known method.
  • a method of performing supercritical drying for example, a method of removing the solvent at a temperature and pressure higher than the critical point of the solvent contained in the wet gel can be mentioned.
  • the whole or a part of the solvent contained in the wet gel is immersed in liquefied carbon dioxide, for example, under the conditions of about 20 to 25 ° C., about 5 to 20 MPa.
  • a method of removing carbon dioxide alone or a mixture of carbon dioxide and a solvent after replacing the solvent with carbon dioxide having a lower critical point than the solvent for example, under the conditions of about 20 to 25 ° C., about 5 to 20 MPa.
  • the airgel composite block or powder obtained by such normal pressure drying or supercritical drying may be additionally dried at 105 to 200 ° C. for about 0.5 to 2 hours under normal pressure. This further facilitates obtaining an airgel having low density and small pores.
  • the additional drying may be performed at 150 to 200 ° C. under normal pressure.
  • Airgel composite powder is obtained by grinding the airgel complex block obtained by drying.
  • the airgel composite block can be placed in a jet mill, a roller mill, a bead mill, a hammer mill, etc., and the operation can be carried out by operating at an appropriate rotation speed and time.
  • the airgel composite powder obtained by the above steps can be applied to various uses by taking advantage of the dispersibility in water, flexibility, adhesion and water repellency.
  • airgel has excellent physical properties because of its high porosity, and it is a heat insulator in the fields of construction, automobiles, home appliances, semiconductors, industrial equipment, etc., acoustic control materials, luminous solar light collectors, gas It can also be used as a filter, catalyst and support material.
  • a dispersion of airgel complex powder it can be used as a water repellent powder.
  • the water repellent treatment method using the water repellent powder is not particularly limited.
  • the adherend can be subjected to water repellent treatment by the following method.
  • the water repellent powder may be brought into direct contact with the surface to be treated of the adherend, or the water repellent treatment liquid containing the water repellent powder may be brought into contact with the surface to be treated of the adherend. Since the water repellent powder of this embodiment has flexibility, the water repellent powder can be disposed on the surface to be treated of the adherend to form the water repellent portion on the surface to be treated.
  • the water repellent treatment of the adherend used as the water repellent treatment liquid containing the water repellent powder of the present embodiment is mainly performed by a process of preparing the water repellent treatment liquid, an application step, a washing step, and a drying step. You may go.
  • a process of preparing the water repellent treatment liquid an application step, a washing step, and a drying step. You may go.
  • each process of the water repellent treatment method using the water repellent treatment liquid according to the present embodiment will be described.
  • the water repellent treatment liquid according to the present embodiment can be prepared by dispersing water repellent powder in a solvent.
  • the water repellent portion can be uniformly formed on the surface to be treated of the target adherend.
  • the water repellent portion may be in a form including at least one of a water repellent film and water repellent particles formed of water repellent powder.
  • solvent water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, acetonitrile, heptane, hexane, toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran
  • organic solvents such as methylene chloride, N, N-dimethylformamide, dimethylsulfoxide, acetic acid, formic acid and the like can be used. You may use an organic solvent individually or in mixture of 2 or more types.
  • the application step is a step of applying a water repellent treatment solution to the surface to be treated.
  • the surface to be treated may be dried after application to evaporate the solvent.
  • a water repellent portion can be formed on the surface to be treated by this step.
  • the water repellent treatment liquid may be applied to the entire surface to be treated or may be selectively applied to a part of the surface to be treated.
  • the thickness of the water repellent portion may be 1 to 500 nm, but may be 20 to 200 nm. By setting the thickness to 1 nm or more, more excellent water repellency can be achieved, and by setting the thickness to 500 nm or less, more excellent flexibility can be achieved.
  • the coating method is not particularly limited, and examples thereof include spin coating, dip coating, spray coating, flow coating, bar coating and gravure coating.
  • the spray coating method is preferable because a water repellent portion can be formed with a uniform thickness even on a surface to be treated having irregularities, the productivity is high, and the use efficiency of the water repellent powder is high.
  • the coating method may be used alone or in combination of two or more.
  • the water repellent portion may be formed on the surface to be treated by applying or immersing the water repellent treatment solution to another substrate (film, cloth, etc.) in advance and then bringing it into contact with the surface to be treated and transferring.
  • the application method can be freely selected according to the amount of use of the water repellent treatment liquid, the area of the surface to be treated, the characteristics and the like.
  • the material which comprises a to-be-processed surface is not specifically limited, For example, metal, ceramics, glass, plastics, and the material (composite material, laminated material etc.) which combined these are mentioned.
  • the water repellent treatment liquid can also be applied to paper, fiber, cloth, non-woven fabric, rubber, leather and the like.
  • the material constituting the surface to be treated may be a water soluble organic compound, a water soluble inorganic compound or the like.
  • the material which comprises a to-be-processed surface is transparent materials, such as glass and plastics.
  • Examples of the metal include stainless steel, aluminum, copper, galvanized steel sheet and iron.
  • Examples of the ceramic include alumina, barium titanate, boron nitride and silicon nitride.
  • Examples of the glass include ordinary soda lime glass, borosilicate glass, alkali-free glass, quartz glass and aluminosilicate glass.
  • plastics include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as polyphenylene carbonate, and aromatic polyester resins such as polyethylene terephthalate (PET).
  • water-soluble organic compounds include glucose, sucrose, starch, polyacrylamide, polyvinyl alcohol and methyl cellulose.
  • water-soluble inorganic compounds include water glass, sodium chloride, sodium phosphate, sodium carbonate, sodium vanadate, sodium borate, potassium chloride, potassium carbonate and sulfuric acid compounds.
  • the adhesion of the water repellent portion can be further improved by drying the surface to be treated to evaporate the solvent.
  • the drying temperature at this time is not particularly limited, and varies depending on the heat resistant temperature of the surface to be treated, but may be 60 to 250 ° C. or 120 to 180 ° C., for example. By setting the temperature to 60 ° C. or more, more excellent adhesion can be achieved, and by setting the temperature to 250 ° C. or less, deterioration due to heat can be suppressed.
  • the washing step is a step of washing the surface to be treated on which the water repellent portion obtained in the coating step is formed. By performing this step, impurities such as unreacted substances and byproducts in the water repellent portion can be reduced, and a water repellent film portion with higher purity can be obtained.
  • the washing step can be repeated, for example, using water and / or an organic solvent. At this time, the washing efficiency can be improved by heating.
  • organic solvent methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, acetonitrile, heptane, hexane, toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran,
  • organic solvents such as methylene chloride, N, N-dimethylformamide, dimethylsulfoxide, acetic acid, formic acid and the like can be used.
  • the above organic solvents may be used alone or in combination of two or more.
  • Organic solvents generally have very low mutual solubility with water. Therefore, in the case of washing with an organic solvent after washing with water, a hydrophilic organic solvent having high mutual solubility in water is preferable.
  • examples of the hydrophilic organic solvent include methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane and the like. Methanol, ethanol, methyl ethyl ketone and the like are excellent in economic point.
  • the amount of water and / or organic solvent used in the washing step can be an amount sufficient to wash the water repellent part, for example, with respect to the total mass of the water repellent part.
  • the amount may be 3 to 10 times.
  • the washing can be repeated until the water content of the surface to be treated becomes 10% by mass or less.
  • the washing temperature may be a temperature equal to or lower than the boiling point of the solvent used for washing, and may be, for example, about 30 to 60 ° C. when using methanol.
  • the heating efficiency can also be improved by heating.
  • a drying process is a process of drying the to-be-processed surface in which the water repellent part wash
  • the drying temperature varies depending on the heat resistant temperature of the surface to be treated and the type of the cleaning solvent.
  • the drying temperature may be, for example, 20 to 250 ° C., or 60 to 180 ° C. from the viewpoint of sufficiently fast evaporation of the solvent and easy to prevent deterioration of the water repellent part.
  • the drying time varies depending on the mass of the water repellent part and the drying temperature, but may be, for example, 1 to 24 hours.
  • the adhesion amount of the water repellent powder on the surface to be treated is preferably one or more per 1 mm square. By using one or more, more excellent water repellency can be achieved.
  • the adhesion amount of the water repellent powder can be calculated using a scanning electron microscope (SEM). For example, in the case of a water repellent powder having an average particle diameter of 100 nm, the area A (1.0 ⁇ 10 ⁇ 4 mm) of a square having a length (1.0 ⁇ 10 ⁇ 2 mm) 100 times the average particle diameter as one side. 2 ) Set. The number B of particles in the square is measured to calculate B / A. This is repeated 10 times, and the average value of B / A obtained is taken as the adhesion amount of particles.
  • SEM scanning electron microscope
  • the water repellent portion formed on the surface to be treated by the water repellent powder can be made into an airgel because it can achieve more excellent water repellency.
  • the airgel formed here is a porous body having nanometer-sized micropores.
  • the airgel is considered to exhibit excellent water repellency because it has few hydroxyl groups on its surface and water hardly enters the fine pores.
  • the airgel has a large porosity, it is considered that a water repellent portion having high transparency can be obtained because the refractive index of the water repellent portion which is the airgel is small.
  • a water repellent portion having excellent water repellency and flexibility can be formed on the surface to be treated by the above-described water repellent treatment method using the water repellent powder of the present embodiment.
  • the water repellent structure in which such a water repellent part is formed can exhibit excellent water repellency and durability.
  • one aspect of the present invention may be a water repellent including airgel composite powder.
  • the form of the water repellent material is not particularly limited, and may be, for example, the above-described water repellent powder, water repellent treatment liquid, or water repellent film.
  • Example 1 [Preparation of water repellent powder 1] 40.0 parts by mass of a carbinol-modified siloxane "X-22-160AS" (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a polysiloxane compound, methyltrimethoxysilane "LS-530" as a silicon compound (Shin-Etsu Chemical Co., Ltd. stock Product name: Product name: 30.0 parts by mass of “MTMS” hereinafter; and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane “KBM-303” (manufactured by Shin-Etsu Chemical Co., Ltd.) 30.
  • the wet gel 1 was transferred to a plastic bottle, sealed, and then pulverized for 10 minutes at 27000 rpm using an Extreme mill (MX-1000XTS manufactured by As One Corporation) to obtain particulate wet gel 1.
  • the resulting particulate wet gel 1 was immersed in 2500 parts by mass of methanol and washed at 60 ° C. for 12 hours. This washing operation was performed a total of three times while changing to fresh methanol.
  • the washed particulate wet gel was immersed in 2500 parts by mass of a low surface tension solvent heptane, and solvent substitution was performed at 40 ° C. for 12 hours. This solvent displacement operation was performed a total of three times while exchanging for fresh heptane.
  • the washed, solvent-replaced particulate wet gel was dried at 40 ° C. under normal pressure for 96 hours and further dried at 150 ° C. for 2 hours.
  • the dried gel is sieved (manufactured by Tokyo Screen Co., Ltd., mesh 45 ⁇ m, wire diameter 32 ⁇ m) to obtain a water repellent powder 1 containing an airgel component having a structure represented by the above general formula (1) and an epoxy group.
  • Example 2 [Preparation of water repellent powder 2] 143.0 parts by mass of ST-OZL-35 (manufactured by Nissan Chemical Industries, Ltd., spherical colloidal silica, average primary particle diameter: 100 nm), 57.0 parts by mass of water, 0.10 parts by mass of acetic acid, CTAB 20.0 parts by mass and 120.0 parts by mass of urea, to which 40.0 parts by mass of the polysiloxane compound A and 30.0 parts by mass of MTMS are added, 3-mercaptopropyltrimethoxysilane "KBM-803" 30.0 mass parts (made by Shin-Etsu Chemical Co., Ltd.) was added, and it was made to react at 25 degreeC for 2 hours, and the sol was obtained.
  • ST-OZL-35 manufactured by Nissan Chemical Industries, Ltd., spherical colloidal silica, average primary particle diameter: 100 nm
  • CTAB 20.0 parts by mass and 120.0 parts by mass of urea to which 40.0
  • the obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, a water repellent powder 2 containing an airgel component having a ladder type structure including the structures represented by the general formulas (2) and (3) and a mercapto group was obtained.
  • the "polysiloxane compound A” was synthesized as follows. First, in a 1-liter three-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser, 100.0 parts by mass of methyl hydroxy-terminated dimethylpolysiloxane "XC 96-723" (manufactured by Momentive, product name), methyl 181.3 parts by mass of trimethoxysilane and 0.50 parts by mass of t-butylamine were mixed and reacted at 30 ° C. for 5 hours. Thereafter, the reaction solution was heated at 140 ° C. for 2 hours under a reduced pressure of 1.3 kPa to remove volatile components, to thereby obtain a bifunctional alkoxy-modified polysiloxane compound (polysiloxane compound A) at both ends.
  • the water repellent liquid 2 was obtained by stirring at 300 rpm for 1 hour using a general-purpose stirrer BL-600 and 5.0 g of the water repellent powder 2 with respect to a mixed solvent of 400.0 g of water and 200.0 g of methanol. .
  • Example 3 [Preparation of water repellent powder 3] 100.0 parts by mass of PL-5L (Sakai Chemical Industry Co., Ltd., coral-shaped colloidal silica, average primary particle diameter: 50 nm), 70.0 parts by mass of water, 0.10 parts by mass of acetic acid, CTAB Mix 20.0 parts by mass, add 20.0 parts by mass of X-22-160AS, 30.0 parts by mass of MTMS, and 20.0 parts by mass of bistrimethoxysilylhexane, and react for 2 hours at 25 ° C. I obtained Sol 3-1.
  • the water repellent liquid 3 was obtained by stirring at 300 rpm for 1 hour using 5.0 g of the water repellent powder 3 and the general-purpose stirrer BL-600 with respect to a mixed solvent of 400.0 g of water and 200.0 g of methanol. .
  • Example 4 [Preparation of water repellent powder 4] 100.0 parts by mass of PL-2L, 100.0 parts by mass of water, 0.10 parts by mass of acetic acid, 20.0 parts by mass of CTAB, 20.0 parts by mass of polysiloxane compound A, and MTMS 30.0 parts by mass and 20.0 parts by mass of bistrimethoxysilylhexane were added, and reacted at 25 ° C. for 2 hours to obtain a sol 4-1.
  • the water repellent solution 4 was obtained by stirring at 300 rpm for 1 hour using a general-purpose stirrer BL-600 and 5.0 g of the water repellent powder 4 with respect to a mixed solvent of 400.0 g of water and 200.0 g of methanol. .
  • Example 5 [Preparation of water repellent powder 5] 100.0 parts by mass of PL-5L, 100.0 parts by mass of water, 0.10 parts by mass of acetic acid, 20.0 parts by mass of CTAB and 120.0 parts by mass of urea are mixed, and this is mixed with X-22- 20.0 parts by mass of 160 AS, 20.0 parts by mass of polysiloxane compound A, 30.0 parts by mass of MTMS, and 30.0 parts by mass of KBM-803 were reacted at 25 ° C. for 2 hours to obtain a sol . The obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, an airgel component having a structure represented by the above general formula (1), a ladder type structure represented by the above general formulas (2) and (3), and a mercapto group Water-repellent powder 5 contained was obtained.
  • the water repellent treatment liquid 5 was obtained by stirring at 300 rpm for 1 hour using 5.0 g of the water repellent powder 5 and the general-purpose stirrer BL-600 with respect to a mixed solvent of 400.0 g of water and 200.0 g of methanol. .
  • Example 2 a water repellent powder 6 containing an airgel component having a ladder type structure represented by the above general formulas (2) and (3) and an amino group was obtained.
  • Example 7 [Preparation of water repellent powder 7] 100.0 parts by mass of PL-2L, 100.0 parts by mass of water, 0.10 parts by mass of acetic acid, 20.0 parts by mass of CTAB, 40.0 parts by mass of polysiloxane compound B, and MTMS The reaction mixture was added with 30.0 parts by mass and allowed to react at 25 ° C. for 2 hours to obtain sol 7-1. 30.0 parts by mass of KBM-603 and 30 parts by mass of water were mixed and reacted at 25 ° C. for 2 hours to obtain a sol 4-2. The sol 4-2 was added to the obtained sol 7-1, gelled at 60 ° C., and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, a water repellent powder 7 containing an airgel component having a ladder type structure represented by the above general formulas (2) and (3) and an amino group was obtained.
  • polysiloxane compound B was synthesized as follows. First, 100.0 parts by mass of XC 96-723, 202.6 parts by mass of tetramethoxysilane, and 0.2 parts by mass of t-butylamine in a 1-liter three-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser. 50 parts by mass were mixed and reacted at 30 ° C. for 5 hours. Thereafter, the reaction solution was heated at 140 ° C. for 2 hours under a reduced pressure of 1.3 kPa to remove volatile components, thereby obtaining a both-end trifunctional alkoxy-modified polysiloxane compound (polysiloxane compound B).
  • Example 8 [Preparation of water repellent powder 8] 143.0 parts by mass of ST-OZL-35, 57.0 parts by mass of water, 20.0 parts by mass of CTAB and 120.0 parts by mass of urea are mixed with 20.0 parts by mass of the polysiloxane compound A , 20.0 parts by mass of DMDMS and 30.0 parts by mass of MTMS, 30.0 parts by mass of 3-acryloxypropyltrimethoxysilane "KBM-5103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and adding at 25 ° C The reaction was carried out for 2 hours to obtain a sol. The obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, a water repellent powder 8 containing an airgel component having a ladder type structure represented by the general formulas (2) and (3) and an acryloyl group was obtained.
  • Example 9 [Preparation of water repellent powder 9] 100.0 parts by mass of PL-5L, 100.0 parts by mass of water, 20.0 parts by mass of CTAB and 120.0 parts by mass of urea are mixed with 20.0 parts by mass of polysiloxane compound A, DMDMS 20.0 parts by mass, 30.0 parts by mass of MTMS, 30.0 parts by mass of 3-methacryloxypropyltrimethoxysilane “KBM-503” (manufactured by Shin-Etsu Chemical Co., Ltd.), and reaction at 25 ° C. for 2 hours
  • the sol was obtained.
  • the obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel.
  • a water repellent powder 9 containing an airgel component having a ladder type structure represented by the above general formulas (2) and (3) and a methacryloyl group was obtained.
  • Example 10 [Preparation of water repellent powder 10] 143.0 parts by mass of ST-OZL-35, 100.0 parts by mass of water, 0.10 parts by mass of acetic acid, and 20.0 parts by mass of CTAB mixed with 20.0 parts by mass of DMDMS, and polysiloxane 20.0 parts by mass of compound A and 50.0 parts by mass of MTMS were added, and reacted at 25 ° C. for 2 hours to obtain sol 10-1. 10.0 parts by mass of KBM-903 and 30 parts by mass of water were mixed and reacted at 25 ° C. for 2 hours to obtain a sol 3-2. The sol 3-2 was added to the obtained sol 10-1, gelled at 60 ° C., and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, a water repellent powder 10 containing an airgel component having a ladder type structure represented by the above general formulas (2) and (3) and an amino group was obtained.
  • the water repellent treatment liquid 10 was obtained by stirring at 300 rpm for 1 hour using a general-purpose stirrer BL-600 and 5.0 g of the water repellent powder 10 with respect to a mixed solvent of 400.0 g of water and 200.0 g of methanol. .
  • Comparative example 1 [Preparation of comparative water repellent powder 1] 200.0 parts by mass of water, 0.10 parts by mass of acetic acid, 20.0 parts by mass of CTAB and 120.0 parts by mass of urea are mixed, 100.0 parts by mass of MTMS are added thereto, and the mixture is stirred at 25.degree. The reaction was carried out to obtain a sol. The obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, a comparative water repellent powder 1 was obtained.
  • Comparative water repellent treatment liquid 1 is obtained by stirring at 300 rpm for 1 hour using a general-purpose stirrer BL-600 and 5.0 g of the comparative water repellent powder 1 against a mixed solvent of 400.0 g of water and 200.0 g of methanol. Although obtained, since the below-mentioned dispersibility evaluation was C, preparation of a water-repellent structure was not completed.
  • Comparative example 2 [Production of comparative water repellent powder 2] 200.0 parts by mass of water, 0.10 parts by mass of acetic acid, 20.0 parts by mass of CTAB and 120.0 parts by mass of urea are mixed, and 100.0 parts by mass of tetraethoxysilane (TEOS) is added thereto The reaction was carried out at 25 ° C. for 2 hours to obtain a sol. The obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. After that, in the same manner as in Example 1, a comparative water repellent powder 2 was obtained.
  • TEOS tetraethoxysilane
  • Comparative water repellent solution 2 is obtained by stirring at 300 rpm for 1 hour using a general-purpose stirrer BL-600 and 5.0 g of the comparative water repellent powder 2 against a mixed solvent of 400.0 g of water and 200.0 g of methanol. Although obtained, since the below-mentioned dispersibility evaluation was C, preparation of a water-repellent structure was not completed.
  • Comparative example 3 [Preparation of comparative water repellent powder 3] 143.0 parts by mass of ST-OZL-35, 100.0 parts by mass of water, 0.10 parts by mass of acetic acid, 20.0 parts by mass of CTAB, and 120.0 parts by mass of urea are mixed, and 20 .0 parts by mass, 20.0 parts by mass of the polysiloxane compound A and 60.0 parts by mass of MTMS were added, and reacted at 25 ° C. for 2 hours to obtain a sol. The obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. After that, in the same manner as in Example 1, a comparative water repellent powder 3 was obtained.
  • Comparative water repellent treatment liquid 3 is obtained by stirring at 300 rpm for 1 hour using a general-purpose stirrer BL-600 and 5.0 g of the comparative water repellent powder 3 against a mixed solvent of 400.0 g of water and 200.0 g of methanol. Although obtained, since the below-mentioned dispersibility evaluation was C, preparation of a water-repellent structure was not completed.
  • Comparative water repellent treatment liquid 4 was obtained by stirring for 1 hour at 300 rpm using 5.0 g of the above comparative water repellent powder 1 with 600.0 g of methyl ethyl ketone (MEK) and a general-purpose stirrer BL-600.
  • MEK methyl ethyl ketone
  • Comparative water repellent structure 4 The slide glass S7213 was dipped in the comparative water repellent treatment liquid 5 for 5 minutes, and then the dip treated slide glass was dried at 120 ° C. under normal pressure for 1 hour to obtain a comparative water repellent structure 4.
  • Comparative example 5 [Preparation of Comparative Water Repellent Treatment Solution 5]
  • a comparative water repellent treatment liquid 5 was obtained by stirring at 300 rpm for 1 hour using 5.0 g of the comparative water repellent powder 2 and 60 g of MEK using a general-purpose stirrer BL-600.
  • Comparative water repellent structure 5 After dipping the slide glass S7213 for 5 minutes in the comparative water repellent treatment solution 5, the dip treated slide glass was dried at 120 ° C. for 1 hour under normal pressure to obtain a comparative water repellent structure 5.
  • Comparative example 6 [Preparation of comparative water repellent treatment solution 6]
  • the comparative water repellent treatment liquid 6 was obtained by stirring at 300 rpm for 1 hour using 5.0 g of the comparative water repellent powder 3 and 60 g of MEK using a general-purpose stirrer BL-600.
  • Comparative water repellent structure 6 The slide glass S7213 was dipped in the comparative water repellent treatment liquid 5 for 5 minutes, and then the dip treated slide glass was dried at 120 ° C. for 1 hour under normal pressure to obtain a comparative water repellent structure 6.
  • Table 1 summarizes the types and addition amounts of Si raw materials in each of the examples and the comparative examples.
  • Compressive Elastic Modulus As a measuring device, a micro compression tester "MCT-510" (product name, manufactured by Shimadzu Corporation) was used. The water repellent powder was set between the upper platen and the lower platen arranged in parallel, and compression was performed at a loading rate of 0.0892 mN / sec. The measurement was terminated when a load of over 4.9 mN was applied or when the measurement sample was destroyed.
  • the compressive elastic modulus was calculated from compressive strain and compressive stress as follows.
  • the compressive strain ⁇ can be obtained by the following equation.
  • ⁇ d the displacement (mm) of the thickness of the measurement sample due to the load
  • d1 the thickness (mm) of the measurement sample before applying the load.
  • the compressive stress ⁇ (MPa) can be determined by the following equation.
  • F indicates a compressive force (N)
  • A indicates a cross-sectional area (mm 2 ) of the measurement sample before loading.
  • ⁇ F / A
  • the compressive elastic modulus E (MPa) can be determined, for example, by the following equation in a compressive force range of 0.1 to 0.2 N.
  • ⁇ 1 represents compressive stress (MPa) measured at a compressive force of 0.1 N
  • ⁇ 2 represents compressive stress (MPa) measured at a compressive force of 0.2 N
  • ⁇ 1 is compressive stress
  • the compressive strain measured at ⁇ 1 is shown
  • ⁇ 2 is the compressive strain measured at compressive stress ⁇ 2 .
  • E ( ⁇ 2 - ⁇ 1 ) / ( ⁇ 2 - ⁇ 1 )
  • abrasion resistance test In the abrasion resistance test, a Kim towel manufactured by Cresia Co., Ltd. was rubbed on the surface of the water repellent structure a plurality of times, and then dried at 105 ° C. for 1 hour to prepare a measurement sample.
  • the contact area of the Kim towel here was 20 mm ⁇ 50 mm, with a weight of 0.1 kg / cm 2 .
  • 2 ⁇ L of ultrapure water droplets were dropped using a contact angle meter DMs-401 manufactured by Kyowa Interface Science Co., Ltd., and the contact angle after 5 seconds was measured at room temperature. The measurement was performed five times, and the average value was taken as the water contact angle.
  • the water repellent powder of the example has high dispersibility in an aqueous solvent as compared to the comparative water repellent powder of the comparative example.
  • the water repellent structure having a water repellent portion formed from the water repellent powder of the example has a large water contact angle and exhibits good water repellency as compared with the water repellent structure of Comparative Examples 4 and 5. It can be confirmed that it has excellent flexibility. Further, as is clear from the results of the abrasion resistance test, the water repellent structure of the example is superior in durability and can maintain good water repellency as compared with the water repellent structure of the comparative example.
  • Example 6 and Comparative Example 6 are compared, by introducing the amino group which is a reactive group, the dispersibility in the aqueous solvent and the water repellency are compatible, and the adhesion is also improved by the abrasion resistance test. Can be confirmed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Silicon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

L'invention concerne une poudre composite d'aérogel contenant un composant d'aérogel et des particules de silice, le composant d'aérogel ayant au moins un groupe polaire choisi dans le groupe constitué par le groupe époxy, le groupe mercapto, le groupe acryloyle, le groupe méthacryloyle et le groupe amino.
PCT/JP2018/037244 2017-10-04 2018-10-04 Poudre composite d'aérogel et matériau hydrofuge Ceased WO2019070035A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-194481 2017-10-04
JP2017194481A JP2019064892A (ja) 2017-10-04 2017-10-04 エアロゲル複合体パウダー及び撥水材

Publications (1)

Publication Number Publication Date
WO2019070035A1 true WO2019070035A1 (fr) 2019-04-11

Family

ID=65994959

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/037244 Ceased WO2019070035A1 (fr) 2017-10-04 2018-10-04 Poudre composite d'aérogel et matériau hydrofuge

Country Status (2)

Country Link
JP (1) JP2019064892A (fr)
WO (1) WO2019070035A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110787745A (zh) * 2019-11-29 2020-02-14 福建六树网络科技有限公司 一种二氧化硅气凝胶复合材料的制备方法及二氧化硅气凝胶复合材料

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023173662A (ja) * 2022-05-26 2023-12-07 宇部エクシモ株式会社 多孔質粒子分散液、多孔質粒子分散液の製造方法、撥水剤、多孔質構造体、及び多孔質構造体の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07196311A (ja) * 1993-11-04 1995-08-01 Eniricerche Spa 多孔性の球状シリカ粒の製法
JP2014167078A (ja) * 2013-02-28 2014-09-11 Panasonic Corp 断熱材成形用組成物、成形体及び成形体の製造方法
WO2016121798A1 (fr) * 2015-01-27 2016-08-04 日立化成株式会社 Procédé de production d'un stratifié d'aérogel et rouleau stratifié d'aérogel
JP2016216283A (ja) * 2015-05-18 2016-12-22 日立化成株式会社 エアロゲル、エアロゲルの製造方法及びエアロゲルフィルム
WO2017002342A1 (fr) * 2015-07-01 2017-01-05 パナソニックＩｐマネジメント株式会社 Aérogel, élément le comprenant et procédé de production associé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07196311A (ja) * 1993-11-04 1995-08-01 Eniricerche Spa 多孔性の球状シリカ粒の製法
JP2014167078A (ja) * 2013-02-28 2014-09-11 Panasonic Corp 断熱材成形用組成物、成形体及び成形体の製造方法
WO2016121798A1 (fr) * 2015-01-27 2016-08-04 日立化成株式会社 Procédé de production d'un stratifié d'aérogel et rouleau stratifié d'aérogel
JP2016216283A (ja) * 2015-05-18 2016-12-22 日立化成株式会社 エアロゲル、エアロゲルの製造方法及びエアロゲルフィルム
WO2017002342A1 (fr) * 2015-07-01 2017-01-05 パナソニックＩｐマネジメント株式会社 Aérogel, élément le comprenant et procédé de production associé

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110787745A (zh) * 2019-11-29 2020-02-14 福建六树网络科技有限公司 一种二氧化硅气凝胶复合材料的制备方法及二氧化硅气凝胶复合材料
CN110787745B (zh) * 2019-11-29 2021-11-05 安徽信义光伏玻璃有限公司 一种二氧化硅气凝胶复合材料的制备方法及二氧化硅气凝胶复合材料

Also Published As

Publication number Publication date
JP2019064892A (ja) 2019-04-25

Similar Documents

Publication Publication Date Title
JP7196854B2 (ja) 塗液、塗膜の製造方法及び塗膜
TWI829911B (zh) 塗液、複合材料及塗膜
JP7156037B2 (ja) 撥水処理剤、撥水構造体及びその製造方法
TWI787318B (zh) 塗液、塗膜的製造方法及塗膜
WO2019069494A1 (fr) Liquide de revêtement, et film de revêtement ainsi que procédé de fabrication de celui-ci
WO2017038777A1 (fr) Composite d'aérogel, matériau de support avec aérogel composite, et matériau thermo-isolant
WO2017168847A1 (fr) Élément doté d'une couche d'aérogel
JPWO2020012553A1 (ja) 塗液及び塗膜
JP7196853B2 (ja) 塗液、塗膜の製造方法及び塗膜
WO2019070035A1 (fr) Poudre composite d'aérogel et matériau hydrofuge
JP7196907B2 (ja) 保温材下腐食の抑制方法、及び保温材下腐食抑制用ペースト
JP7156038B2 (ja) 粒子処理用の処理剤、撥水性粒子及びその製造方法、撥水層並びに浸透防止構造体
JP7160106B2 (ja) エアロゲル粒子、分散体及び塗膜
WO2017038781A1 (fr) Complexe d'aérogel
WO2019069405A1 (fr) Dispersion liquide, et particules d'aérogel
WO2018143361A1 (fr) Poudre hydrofuge

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18863882

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18863882

Country of ref document: EP

Kind code of ref document: A1