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WO2017038777A1 - Composite d'aérogel, matériau de support avec aérogel composite, et matériau thermo-isolant - Google Patents

Composite d'aérogel, matériau de support avec aérogel composite, et matériau thermo-isolant Download PDF

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Publication number
WO2017038777A1
WO2017038777A1 PCT/JP2016/075226 JP2016075226W WO2017038777A1 WO 2017038777 A1 WO2017038777 A1 WO 2017038777A1 JP 2016075226 W JP2016075226 W JP 2016075226W WO 2017038777 A1 WO2017038777 A1 WO 2017038777A1
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Prior art keywords
group
airgel
airgel composite
mass
support member
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PCT/JP2016/075226
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English (en)
Japanese (ja)
Inventor
知里 吉川
竜也 牧野
智彦 小竹
寛之 泉
正人 宮武
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Resonac Corp
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Hitachi Chemical Co Ltd
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Priority to JP2017538025A priority Critical patent/JP6269903B2/ja
Publication of WO2017038777A1 publication Critical patent/WO2017038777A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • 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
    • 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
    • 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

Definitions

  • the present disclosure relates to an airgel composite, a support member with an airgel composite, and a heat insulating material.
  • Silica airgel is known as a material having low thermal conductivity and heat insulation. Silica airgel is useful as a functional material having excellent functionality (thermal insulation, etc.), unique optical properties, and unique electrical properties. For example, an electronic substrate utilizing the ultra-low dielectric constant properties of silica airgel It is used as a material, a heat insulating material using the high heat insulating property of silica airgel, a light reflecting material using the ultra-low refractive index of silica airgel, and the like.
  • a supercritical drying method in which a gel-like compound (alcogel) obtained by hydrolyzing and polymerizing alkoxysilane is dried under supercritical conditions of a dispersion medium.
  • an alcogel and a dispersion medium solvent used for drying
  • the dispersion medium is applied to the supercritical fluid by applying a temperature and pressure above its critical point to form a supercritical fluid. It is a method of removing the solvent.
  • the supercritical drying method requires a high-pressure process, capital investment is required for a special apparatus that can withstand supercriticality, and much labor and time are required.
  • the obtained airgel is poor in handling and large in size. Because it is difficult, there is a problem in productivity. For example, the agglomerated airgel obtained by the above process may be broken simply by trying to lift it by hand. This is presumably due to the fact that the density of the airgel is low and that the airgel has a pore structure in which fine particles of about 10 nm are weakly connected.
  • the present disclosure has been made in view of the above circumstances, and an object thereof is to provide an airgel composite excellent in heat insulation and flexibility.
  • the present disclosure also provides a support member with an airgel composite formed by supporting such an airgel composite, and a heat insulating material.
  • the present inventor has excellent heat insulation and flexibility as long as the airgel composite is a composite of silica particles having a predetermined number of silanol groups in the airgel. It was found to be expressed.
  • the present disclosure relates to silica particles having a silanol group number of 10 ⁇ 10 18 to 1000 ⁇ 10 18 / g, a silicon compound having a hydrolyzable functional group or a condensable functional group, and a hydrolyzable functional group
  • An airgel composite that is a dried product of a wet gel that is a condensate of a sol containing at least one selected from the group consisting of hydrolyzed products of silicon compounds having the following.
  • the airgel composite of the present disclosure is excellent in heat insulation and flexibility, unlike the airgel obtained by the prior art.
  • the hydrolyzable functional group may be an alkoxy group.
  • the alkoxy group may have 1 to 6 carbon atoms.
  • the condensable functional group may be a hydroxyalkyl group.
  • the number of carbon atoms in the hydroxyalkyl group can be 1-6.
  • the silicon compound can contain a polysiloxane compound having a hydrolyzable functional group or a condensable functional group.
  • the polysiloxane compound can include a compound having a structure represented by the following general formula (B).
  • 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 represents an integer of 1 to 50.
  • the airgel composite may have a ladder structure including a support portion and a bridge portion, and the bridge portion may have a structure represented by the following general formula (2).
  • R 5 and R 6 each independently represents an alkyl group or an aryl group, and b represents an integer of 1 to 50.
  • the airgel composite can have a ladder structure represented by the following general formula (3).
  • R 5 , R 6 , R 7 and R 8 each independently represents an alkyl group or an aryl group
  • a and c each independently represents an integer of 1 to 3000
  • b is 1 to 50 Indicates an integer.
  • the average primary particle diameter of the silica particles can be 1 to 500 nm. Thereby, it becomes easy to improve heat insulation and a softness
  • the shape of the silica particles can be spherical.
  • the silica particles can be colloidal silica particles. Thereby, further excellent heat insulation and flexibility can be achieved.
  • the dried product can be obtained by drying at a temperature below the critical point of the solvent used for drying the wet gel and under atmospheric pressure. This makes it easier to obtain an airgel composite that is excellent in heat insulation and flexibility.
  • the present disclosure further provides a support member with an airgel composite comprising the airgel composite and a support member supporting the airgel composite.
  • the airgel composite since the airgel composite has excellent heat insulating properties and flexibility, it can exhibit excellent heat insulating properties and excellent flexibility that is difficult to achieve with conventional airgels.
  • the present disclosure further provides a heat insulating material including the airgel composite.
  • the heat insulating material according to the present disclosure exhibits excellent heat insulating properties and excellent flexibility that is difficult to achieve with conventional heat insulating materials because the airgel composite has excellent heat insulating properties and flexibility. Can do.
  • an airgel composite excellent in heat insulation and flexibility can be provided. That is, it is possible to provide an airgel composite that exhibits excellent heat insulating properties, improves handleability, can be increased in size, and can increase productivity. Thus, the airgel composite excellent in heat insulation and flexibility has a possibility of being used for various purposes. According to the present disclosure, it is also possible to provide a support member with an airgel composite formed by supporting such an airgel composite, and a heat insulating material.
  • an important point according to the present disclosure is that it becomes easier to control heat insulation and flexibility than conventional aerogels. This is not possible with conventional aerogels that require sacrificing thermal insulation to obtain flexibility or sacrificing flexibility to obtain thermal insulation.
  • excellent in heat insulation and flexibility does not necessarily mean that both numerical values representing both characteristics are high. For example, “excellent flexibility while maintaining good heat insulation” , “Excellent thermal insulation while maintaining good flexibility” and the like.
  • the surface of the airgel composite in the foil-like support member with the airgel composite obtained in Example 4 is (a) 10,000 times, (b) 50,000 times, (c) 200,000 times, and (d) 350,000. It is the SEM image observed by each magnification.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value of a numerical range in a certain step may be replaced with the upper limit value or the lower limit value of a numerical range in another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • “A or B” only needs to include either A or B, and may include both.
  • the materials exemplified in the present specification can be used singly or in combination of two or more unless otherwise specified.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. means.
  • the obtained low-density dried gel is referred to as “aerogel” regardless of the drying method of the wet gel.
  • the airgel means “a gel composed of a microporous solid whose dispersed phase is a gas”, which is an aerogel in a broad sense, that is, “Gel compressed of a microporous solid in which the dispersed phase is a gas”. To do.
  • the inside of an airgel has a network-like fine structure, and has a cluster structure in which airgel particles of about 2 to 20 nm (particles constituting the airgel) are bonded. There are pores less than 100 nm between the skeletons formed by these clusters. Thereby, 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 airgel include so-called organic-inorganic hybrid silica airgel into which an organic group (such as a methyl group) or an organic chain is introduced.
  • the airgel composite of the present embodiment has a cluster structure that is a feature of the above airgel while silica particles are composited in the airgel, and has a three-dimensionally fine porous structure. ing.
  • the airgel composite of this embodiment contains an airgel component and silica particles. Although not necessarily meaning the same concept as this, the airgel composite of the present embodiment can also be expressed as containing silica particles as a component constituting the three-dimensional network skeleton. .
  • the airgel composite of this embodiment is excellent in heat insulation and flexibility as described later. In particular, since the flexibility is excellent, the handling property as an airgel composite is improved and the size can be increased, so that the productivity can be increased. In addition, such an airgel composite is obtained by making silica particles exist in the airgel production environment.
  • the merit by the presence of silica particles is not only that the heat insulation and flexibility of the composite itself can be improved, but also shortening the time of the wet gel generation process described later, or simplifying the drying process from the washing and solvent replacement process. Is also possible. In addition, shortening of the time of this process and simplification of a process are not necessarily calculated
  • the composite aspect of an airgel component and a silica particle is various.
  • the airgel component may be in an indeterminate form such as a film or may be in the form of particles (aerogel particles).
  • the airgel component since the airgel component is in various forms and exists between the silica particles, it is presumed that flexibility is imparted to the skeleton of the composite.
  • the composite mode of the airgel component and the silica particles includes a mode in which an amorphous airgel component is interposed between the silica particles.
  • a mode in which an amorphous airgel component is interposed between the silica particles specifically, for example, an embodiment in which silica particles are coated with a film-like airgel component (silicone component) (an embodiment in which the airgel component encloses silica particles), the airgel component serves as a binder, and the silica particles , A mode in which the airgel component is filled with a plurality of silica particle gaps, a mode of a combination of these modes (a mode in which silica particles arranged in a cluster are coated with the airgel component, etc.) An embodiment is mentioned.
  • the airgel composite can have a three-dimensional network skeleton composed of silica particles and an airgel component (silicone component), and there is no particular limitation on the specific mode (form).
  • the airgel component may be in the form of a clear particle as shown in FIG.
  • the mechanism by which such various aspects occur in the airgel composite of the present embodiment is not necessarily clear, but the present inventor speculates that the generation rate of the airgel component in the gelation process is involved.
  • the production speed of the airgel component tends to vary by varying the number of silanol groups in the silica particles.
  • the production rate of the airgel component also tends to fluctuate by changing the pH of the system.
  • the aspect of the airgel composite (size, shape, etc. of the three-dimensional network skeleton) can be controlled by adjusting the size, shape, silanol group number, system pH, etc. of the silica particles. Therefore, it is considered that the density, porosity, etc. of the airgel composite can be controlled, and the heat insulating property and flexibility of the airgel composite can be controlled.
  • the three-dimensional network skeleton of the airgel composite may be composed of only one kind of the various aspects described above, or may be composed of two or more kinds of aspects.
  • FIG. 1 the airgel composite of the present embodiment will be described using FIG. 1 as an example.
  • the present disclosure is not limited to the aspect of FIG.
  • the following descriptions can be referred to as appropriate.
  • FIG. 1 is a diagram schematically illustrating a fine structure of an airgel composite according to an embodiment of the present disclosure.
  • the airgel composite 10 includes a three-dimensional network skeleton formed by the airgel particles 1 constituting the airgel component being partially linked in a three-dimensional manner through silica particles 2; And pores 3 surrounded by the skeleton.
  • the silica particles 2 are interposed between the airgel particles 1 and function as a skeleton support that supports the three-dimensional network skeleton. Therefore, it is thought that by having such a structure, moderate strength is imparted to the airgel while maintaining the heat insulation and flexibility as the airgel.
  • the airgel composite may have a three-dimensional network skeleton formed by three-dimensionally connecting silica particles randomly through the airgel particles.
  • Silica particles may be covered with airgel particles.
  • the said airgel particle (aerogel component) is comprised from a silicon compound, it is guessed that the affinity to a silica particle is high. Therefore, in this embodiment, it is considered that the silica particles were successfully introduced into the three-dimensional network skeleton of the airgel. In this respect, it is considered that the silanol groups of the silica particles also contribute to the affinity between them.
  • the airgel particle 1 is considered to be in the form of secondary particles composed of a plurality of primary particles, and is generally spherical.
  • the airgel particle 1 may have an average particle size (that is, a secondary particle size) of 2 nm or more, may be 5 nm or more, and may be 10 nm or more.
  • the said average particle diameter can be 50 micrometers or less, may be 2 micrometers or less, and may be 200 nm or less. That is, the average particle diameter can be 2 nm to 50 ⁇ m, but may be 5 nm to 2 ⁇ m, or 10 nm to 200 nm.
  • an airgel composite having excellent flexibility can be easily obtained.
  • the average particle diameter of the primary particles constituting the airgel particles 1 can be set to 0.1 nm to 5 ⁇ m from the viewpoint of easy formation of secondary particles having a low density porous structure. It may be 200 nm, or 1 nm to 20 nm.
  • the silica particles 2 can be used without any particular limitation, and examples thereof include amorphous silica particles. Further, 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 monodispersibility and are easy to suppress aggregation in the sol. Note that 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 a spherical shape, a cage shape, and an association type. Of these, the 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 nm or more, may be 5 nm or more, and may be 20 nm or more.
  • the average primary particle diameter can be 500 nm or less, 300 nm or less, or 100 nm or less. That is, the average primary particle diameter can be 1 to 500 nm, but may be 5 to 300 nm, or 20 to 100 nm.
  • the average primary particle diameter of the silica particles 2 is 1 nm or more, it becomes easy to impart an appropriate strength to the airgel, and an airgel composite having excellent shrinkage resistance during drying is easily obtained.
  • the average primary particle diameter is 500 nm or less, it becomes easy to suppress the solid heat conduction of the silica particles, and it becomes easy to obtain an airgel composite excellent in heat insulation.
  • the airgel particle 1 (aerogel component) and the silica particle 2 are bonded in the form of hydrogen bonding and / or chemical bonding.
  • hydrogen bonds and / or chemical bonds are considered to be formed by the silanol groups and / or reactive groups of the airgel particles 1 (aerogel components) and the silanol groups of the silica particles 2. Therefore, it is thought that moderate strength is easily imparted to the airgel when the bonding mode is chemical bonding.
  • the particles to be combined with the airgel component are not limited to silica particles, and inorganic particles or organic particles having a silanol group on the particle surface can also be used.
  • the number of silanol groups per gram of the silica particles 2 is 10 ⁇ 10 18 pieces / g or more, but may be 50 ⁇ 10 18 pieces / g or more, or 100 ⁇ 10 18 pieces / g or more. .
  • the number of silanol groups is 1000 ⁇ 10 18 pieces / g or less, but may be 800 ⁇ 10 18 pieces / g or less, or 700 ⁇ 10 18 pieces / g or less. That is, the number of silanol groups is 10 ⁇ 10 18 to 1000 ⁇ 10 18 / g, but may be 50 ⁇ 10 18 to 800 ⁇ 10 18 / g, or 100 ⁇ 10 18 to 700 ⁇ 10. 18 pieces / g may be sufficient.
  • the number of silanol groups per gram of silica particles 2 is 10 ⁇ 10 18 pieces / g or more, so that the airgel composite can have better reactivity with the airgel particles 1 (airgel component) and has excellent shrinkage resistance. It becomes easy to obtain a body.
  • the number of silanol groups is 1000 ⁇ 10 18 / g or less, it is easy to suppress abrupt gelation at the time of sol preparation, and it becomes easy to obtain a homogeneous airgel composite.
  • the number of silanol groups in the silica particles can be measured as follows. [1] First, 15 g of silica particles are weighed into a container (X [g]) whose mass has been measured and dispersed in an appropriate amount (100 ml or less) of water. In the case of a dispersion in which silica particles are dispersed in a medium such as water, the dispersion is weighed in a container so that the silica particles are 15 g. [2] Next, the pH of the dispersion is adjusted to 3.0 to 3.5 with 0.1 mol / L hydrochloric acid. The mass (Y [g]) at this time is measured to determine the total mass (YX [g]) of the dispersion.
  • [3] Disperse an amount of dispersion ((YX) / 10 [g]) corresponding to 1/10 of the total mass obtained in [2] above into another container. At this stage, the amount of silica particles (A [g]) contained in the dispersion is 1.5 g.
  • [4] Add 30 g of sodium chloride, and then add ultrapure water to make the total amount 150 g. This is adjusted to pH 4.0 with a 0.1 mol / L sodium hydroxide aqueous solution to obtain a sample for titration.
  • the BET specific surface area S BET of the silica particles can be determined according to the BET specific surface area method (gas adsorption method).
  • a specific measuring method for example, a one-point method or a multi-point method for adsorbing nitrogen gas using a BET specific surface area measuring device (gas adsorption amount measuring device) for silica particles sufficiently vacuum degassed at 250 ° C. It can ask for.
  • the silica particles may be dried using a vacuum freeze dryer. The silica particles after drying are finely crushed with a mortar or the like to obtain a sample for measurement.
  • the average particle size of particles is determined using an airgel composite using a scanning electron microscope (hereinafter abbreviated as “SEM”). It can be obtained by directly observing the cross section of the body.
  • SEM scanning electron microscope
  • the particle diameter of each airgel particle or silica particle can be obtained from the three-dimensional network skeleton based on the diameter of the cross section.
  • the diameter here means the diameter when the cross section of the skeleton forming the three-dimensional network skeleton 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 having the same area.
  • the average particle diameter the diameter of a circle is obtained for 100 particles, and the average is taken.
  • the biaxial average primary particle diameter is calculated as follows from the result of observing 20 arbitrary particles by SEM. That is, in the case of colloidal silica particles having a solid concentration of 5 to 40% by mass normally dispersed in water, for example, a chip with a 2 cm square wafer with a pattern wiring is immersed in the dispersion of colloidal silica particles for about 30 seconds. Thereafter, the chip is rinsed with pure water for about 30 seconds and blown with nitrogen.
  • the chip is placed on a sample stage for SEM observation, an acceleration voltage of 10 kV is applied, the silica particles are observed at a magnification of 100,000, and an image is taken.
  • 20 silica particles are arbitrarily selected from the obtained image, and the average of the particle diameters of these particles is defined as the average particle diameter.
  • a rectangle (circumscribed rectangle L) circumscribing the silica particle 2 and arranged so that the long side is the longest is led.
  • the long side of the circumscribed rectangle L is X
  • the short side is Y
  • the biaxial average primary particle diameter is calculated as (X + Y) / 2, and is defined as the particle diameter of the particle.
  • the size of the pores 3 in the airgel composite will be described in the section of [Density and porosity] described later.
  • the content of the airgel component contained in the airgel composite can be 4 parts by mass or more with respect to 100 parts by mass of the total amount of the airgel composite, but may be 10 parts by mass or more. Moreover, although the said content can be 25 mass parts or less, it may be 20 mass parts or less. That is, the content can be 4 to 25 parts by mass, but may be 10 to 20 parts by mass. When the content is 4 parts by mass or more, an appropriate strength is easily imparted, and when the content is 25 parts by mass or less, good heat insulating properties are easily obtained.
  • the content of the silica particles contained in the airgel composite can be 1 part by mass or more with respect to 100 parts by mass of the total amount of the airgel composite, but may be 3 parts by mass or more. Moreover, although the said content can be 25 mass parts or less, it may be 15 mass parts or less. That is, the content can be 1 to 25 parts by mass, but may be 3 to 15 parts by mass. When the content is 1 part by mass or more, an appropriate strength is easily imparted to the airgel composite, and when the content is 25 parts by mass or less, solid heat conduction of the silica particles is easily suppressed.
  • the airgel composite may further contain other components such as carbon graphite, aluminum compound, magnesium compound, silver compound, and titanium compound for the purpose of suppressing heat radiation.
  • the content of other components is not particularly limited, but can be 1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the airgel complex from the viewpoint of sufficiently securing the desired effect of the airgel complex.
  • the airgel composite of the present embodiment comprises the above silica particles having a silanol group number of 10 ⁇ 10 18 to 1000 ⁇ 10 18 / g, and a hydrolyzable functional group or a condensable functional group (in the molecule).
  • a dried product of a wet gel that is a condensate of a sol containing at least one selected from the group consisting of a silicon compound having a hydrolyzable functional group and a hydrolysis product of a silicon compound having a hydrolyzable functional group (generated from the sol Obtained by drying the wet gel).
  • the silicon compound having a hydrolyzable functional group or a condensable functional group a silicon compound (silicon compound) other than the polysiloxane compound described later can be used. That is, the sol is a group consisting of a hydrolyzable functional group or a silicon compound having a condensable functional group (excluding a polysiloxane compound) and a hydrolyzed product of the silicon compound having a hydrolyzable functional group. It may contain at least one compound selected from the following (hereinafter, sometimes referred to as “silicon compound group”). The number of silicon atoms in the molecule of 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.
  • Alkyl silicon alkoxide can make the number of hydrolyzable functional groups 3 or less from the viewpoint of improving water resistance.
  • alkyl silicon alkoxides include monoalkyltrialkoxysilanes, monoalkyldialkoxysilanes, dialkyldialkoxysilanes, monoalkylmonoalkoxysilanes, dialkylmonoalkoxysilanes, and trialkylmonoalkoxysilanes.
  • Examples thereof include methyltrimethoxysilane, methyldimethoxysilane, dimethyldimethoxysilane, and ethyltrimethoxysilane.
  • Examples of the hydrolyzable functional group include alkoxy groups such as methoxy group and ethoxy group.
  • the silicon compound having a condensable functional group is not particularly limited.
  • silane tetraol, methyl silane triol, dimethyl silane diol, phenyl silane triol, phenyl methyl silane diol, diphenyl silane diol, n-propyl silane triol examples include hexyl silane triol, octyl silane triol, decyl silane triol, and trifluoropropyl silane triol.
  • a silicon compound having a hydrolyzable functional group or a condensable functional group is a reactive group different from the hydrolyzable functional group and the condensable functional group (hydrolyzable functional group and condensable functional group). It may further have a functional group (not applicable).
  • the reactive group include an epoxy group, a mercapto group, a glycidoxy group, a vinyl group, an acryloyl group, a methacryloyl group, and an amino group.
  • the epoxy group may be contained in an epoxy group-containing group such as a glycidoxy group.
  • the number of hydrolyzable functional groups is 3 or less, and as a silicon compound having a reactive group, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, N-phenyl-3-amino Propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like can also be used.
  • vinylsilane triol 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 a hydrolyzable functional group at the molecular end of 3 or less can also be used.
  • the silicon compound having a hydrolyzable functional group or a condensable functional group, and the hydrolysis product of the silicon compound having a hydrolyzable functional group may be used alone or in combination of two or more. Good.
  • 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-described silicon compound is obtained by hydrolyzing a polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a polysiloxane compound having a hydrolyzable functional group. It may further contain at least one selected from the group consisting of decomposition products (hereinafter sometimes referred to as “polysiloxane compound group”).
  • the functional group in the polysiloxane compound or the like is not particularly limited, but can be a group that reacts with the same functional group or reacts with another functional group.
  • Examples of the hydrolyzable functional group include an alkoxy group.
  • Examples of the condensable 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 above-mentioned reactive group (hydrolyzable functional group and condensation) different from the hydrolyzable functional group and the condensable functional group. May further have a functional group that does not correspond to a functional functional group).
  • These polysiloxane compounds having a functional group and a reactive group may be used alone or in combination of two or more.
  • examples of the group that improves the flexibility of the airgel composite include an alkoxy group, a silanol group, and a hydroxyalkyl group.
  • an alkoxy group and a hydroxyalkyl group Can further improve the compatibility of the sol.
  • the number of carbon atoms of the alkoxy group and hydroxyalkyl group can be 1 to 6, but the flexibility of the airgel composite is not limited. It may be 2 to 4 from the viewpoint of further improving.
  • Examples of the polysiloxane compound having a hydroxyalkyl group include those having a structure represented by the following general formula (A).
  • R 1a represents a hydroxyalkyl group
  • R 2a represents an alkylene group
  • R 3a and R 4a each independently represents an alkyl group or an aryl group
  • n represents an integer of 1 to 50.
  • examples of the aryl group include a phenyl group and a substituted phenyl group.
  • examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
  • two R 1a s may be the same or different, and similarly, two R 2a s may be the same or different.
  • two or more R 3a s may be the same or different, and similarly two or more R 4a s may be the same or different.
  • R 1a includes a hydroxyalkyl group having 1 to 6 carbon atoms, 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 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.
  • n can be 2 to 30, but may be 5 to 20.
  • polysiloxane compound having the structure represented by the general formula (A) a commercially available product can be used, and compounds such as X-22-160AS, KF-6001, KF-6002, and KF-6003 (all of them) , Manufactured by Shin-Etsu Chemical Co., Ltd.), compounds such as XF42-B0970, Fluid OFOH 702-4% (all manufactured by Momentive).
  • Examples of the polysiloxane compound having an alkoxy group include those having a structure represented by the following general formula (B).
  • 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 represents an integer of 1 to 50.
  • examples of the aryl group include a phenyl group and a substituted phenyl group.
  • examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
  • two R 1b s may be the same or different from each other, and two R 2b s may be the same or different from each other, and similarly two R 1b s. 3b may be the same or different.
  • m is an integer of 2 or more
  • two or more R 4b s may be the same or different
  • similarly two or more R 5b s are each the same. May be different.
  • examples of R 1b include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the like.
  • alkyl group or alkoxy group A methyl group, a methoxy group, an ethoxy group, etc. are mentioned.
  • R 2b and R 3b each independently include an alkoxy group having 1 to 6 carbon atoms, and examples of the alkoxy group include a methoxy group and an ethoxy group.
  • 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 the structure represented by the general formula (B) can be obtained by appropriately referring to the production methods reported in, for example, JP-A Nos. 2000-26609 and 2012-233110. Can do.
  • the polysiloxane compound having an alkoxy group may exist as a hydrolysis product in the sol, and the polysiloxane compound having an alkoxy group and the hydrolysis product are mixed. You may do it.
  • the polysiloxane compound having an alkoxy group all of the alkoxy groups in the molecule may be hydrolyzed or partially hydrolyzed.
  • polysiloxane compounds having hydrolyzable functional groups or condensable functional groups and the hydrolysis products of polysiloxane compounds having hydrolyzable functional groups may be used alone or in combination of two or more. May be used.
  • Content of silicon compound group contained in the sol (content of silicon compound having hydrolyzable functional group or condensable functional group, and hydrolysis product of silicon compound having hydrolyzable functional group)
  • the sum of the contents) can be 5 parts by mass or more with respect to 100 parts by mass of the sol, and may be 10 parts by mass or more.
  • the content can be 50 parts by mass or less, or 30 parts by mass or less with respect to 100 parts by mass of the total amount of sol. That is, the content of the silicon compound group can be 5 to 50 parts by mass with respect to 100 parts by mass of the sol, but may be 10 to 30 parts by mass.
  • the content of the silicon compound group and the content of the polysiloxane compound group (content of the polysiloxane compound having a hydrolyzable functional group or a condensable functional group)
  • the total content of hydrolysis products of polysiloxane compounds having hydrolyzable functional groups can be 5 parts by mass or more with respect to 100 parts by mass of the sol. Or more.
  • the total content can be 50 parts by mass or less, or 30 parts by mass or less, with respect to 100 parts by mass of the total amount of sol. That is, the total content may be 5 to 50 parts by mass with respect to 100 parts by mass of the sol, but may be 10 to 30 parts by mass.
  • the ratio of the content of the silicon compound group and the content of the polysiloxane compound group may be 0.5: 1 to 4: 1, but may be 1: 1 to 2: 1. .
  • the ratio of the content of these compounds is 0.5: 1 or more, good compatibility is further easily obtained, and when the ratio is 4: 1 or less, gel shrinkage is further easily suppressed.
  • the content of the silica particles contained in the sol can be 1 part by mass or more with respect to 100 parts by mass of the total amount of the sol, and may be 4 parts by mass or more.
  • the content can be 20 parts by mass or less, or 15 parts by mass or less, with respect to 100 parts by mass of the total amount of sol. That is, the content of silica particles 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 airgel composite of the present embodiment comprises the above silica particles having a silanol group number of 10 ⁇ 10 18 to 1000 ⁇ 10 18 / g, and a hydrolyzable functional group or a condensable functional group (in the molecule).
  • the condensate may be obtained by a condensation reaction of a hydrolysis product obtained by hydrolysis of a silicon compound having a hydrolyzable functional group, and is not a functional group obtained by hydrolysis. It may be obtained by a condensation reaction of a silicon compound having a functional group of The silicon compound only needs to have at least one of a hydrolyzable functional group and a condensable functional group, and may have both a hydrolyzable functional group and a condensable functional group.
  • the airgel composite of this embodiment can contain a polysiloxane having a main chain including a siloxane bond (Si—O—Si).
  • the airgel composite may have the following M unit, D unit, T unit or Q unit as a structural unit.
  • R represents an atom (hydrogen atom or the like) or an atomic group (alkyl group or the like) bonded to a silicon atom.
  • the M unit is a unit composed of a monovalent group in which a silicon atom is bonded to one oxygen atom.
  • the D unit is a unit composed of a divalent group in which a silicon atom is bonded to two oxygen atoms.
  • the T unit is a unit composed of a trivalent group in which a silicon atom is bonded to three oxygen atoms.
  • the Q unit is a unit composed 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 composite of the present embodiment include the following modes. By adopting these aspects, it becomes easy to control the heat insulating property and flexibility of the airgel composite to a desired level. By employ
  • the airgel composite of this embodiment can have a structure represented by the following general formula (1).
  • the airgel composite of this embodiment can have a structure represented by the following general formula (1a) as a structure including the structure represented by the formula (1).
  • the structures represented by the formulas (1) and (1a) can be introduced into the skeleton of the airgel composite.
  • 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.
  • examples of the aryl group include a phenyl group and a substituted phenyl group.
  • the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
  • p represents an integer of 1 to 50.
  • two or more R 1 s may be the same or different, and similarly, two or more R 2 s may be the same or different.
  • 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 include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like. And a methyl group.
  • R 3 and R 4 each independently include an alkylene group having 1 to 6 carbon atoms, and examples of the alkylene group include an ethylene group and a propylene group. Is mentioned.
  • p can be 2 to 30, and can be 5 to 20.
  • the airgel composite of the present embodiment is an airgel composite having a ladder type structure including a column portion and a bridge portion, and the airgel composite having a structure in which the bridge portion is represented by the following general formula (2).
  • a ladder structure as an airgel component into the skeleton of the airgel composite, heat resistance and mechanical strength can be improved.
  • the polysiloxane compound having the structure represented by the general formula (B) By using the polysiloxane compound having the structure represented by the general formula (B), a ladder structure having a bridge portion represented by the general formula (2) is introduced into the skeleton of the airgel composite.
  • the “ladder structure” has two struts and bridges connecting the struts (having a so-called “ladder” form). It is.
  • the skeleton of the airgel composite may have a ladder structure, but the airgel composite may partially have a ladder structure.
  • R 5 and R 6 each independently represents an alkyl group or an aryl group, and b represents an integer of 1 to 50.
  • examples of the aryl group include a phenyl group and a substituted phenyl group.
  • examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
  • b is an integer of 2 or more
  • two or more R 5 s may be the same or different, and similarly two or more R 6 s are each the same. May be different.
  • silsesquioxane is a polysiloxane having a composition 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 bridging portion is —O— (having the T unit as a structural unit).
  • the structure of the bridge portion is a structure (polysiloxane structure) represented by the general formula (2).
  • the airgel of the present embodiment may further have a structure derived from silsesquioxane in addition to the structures represented by the general formulas (1) to (3).
  • R represents a hydroxy group, an alkyl group or an aryl group.
  • the ladder structure has the following general formula ( It may have a ladder structure represented by 3).
  • R 5 , R 6 , R 7 and R 8 each independently represents an alkyl group or an aryl group
  • a and c each independently represents an integer of 1 to 3000
  • b is 1 to 50 Indicates an integer.
  • examples of the aryl group include a phenyl group and a substituted phenyl group.
  • examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
  • b is an integer of 2 or more
  • two or more R 5 s may be the same or different
  • similarly two or more R 6 s are each the same. May be different.
  • when a is an integer of 2 or more
  • two or more R 7 s may be the same or different.
  • when c is an integer of 2 or more, 2 or more R 8 may be the same or different.
  • R 5 , R 6 , R 7 and R 8 (however, R 7 and R 8 are only in formula (3)) Each independently includes 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.
  • 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 of the present embodiment can have a structure represented by the following general formula (4).
  • the airgel composite of the present embodiment contains silica particles and can have a structure represented by the following general formula (4).
  • R 9 represents an alkyl group.
  • examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group include a methyl group.
  • the airgel composite of the present embodiment can have a structure represented by the following general formula (5).
  • the airgel composite of the present embodiment contains silica particles and can have a structure represented by the following general formula (5).
  • R 10 and R 11 each independently represent an alkyl group.
  • examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group include a methyl group.
  • the airgel composite of this embodiment can have a structure represented by the following general formula (6).
  • the airgel composite of the present embodiment contains silica particles and can have a structure represented by the following general formula (6).
  • 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 an ethylene group and a hexylene group.
  • the thermal conductivity at 25 ° C. under atmospheric pressure can be 0.03 W / m ⁇ K or less, but may be 0.025 W / m ⁇ K or less, or It may be 0.02 W / m ⁇ K or less.
  • the lower limit value of the thermal conductivity is not particularly limited, but can be set to 0.01 W / m ⁇ K, for example.
  • Thermal conductivity can be measured by a steady method. Specifically, it can be measured using, for example, a steady-state thermal conductivity measuring device “HFM436 Lambda” (manufactured by NETZSCH, product name, HFM436 Lambda is a registered trademark).
  • HFM436 Lambda manufactured by NETZSCH, product name, HFM436 Lambda is a registered trademark.
  • the outline of the thermal conductivity measurement method using the steady method thermal conductivity measuring apparatus is as follows.
  • the airgel composite is processed into a size of 150 mm ⁇ 150 mm ⁇ 100 mm using a blade having a blade angle of about 20 to 25 degrees to obtain a measurement sample.
  • the recommended sample size in HFM436Lambda is 300 mm ⁇ 300 mm ⁇ 100 mm
  • the thermal conductivity when measured with the above sample size is the same value as the thermal conductivity when measured with the recommended sample size. Confirmed.
  • the measurement sample is shaped with a sandpaper of # 1500 or more as necessary. Then, before the thermal conductivity measurement, the measurement sample is dried at 100 ° C.
  • the measurement conditions are an atmospheric pressure and an average temperature of 25 ° C.
  • the measurement sample obtained as described above is sandwiched between the upper and lower heaters with a load of 0.3 MPa, the temperature difference ⁇ T is set to 20 ° C., and the guard sample is adjusted so as to obtain a one-dimensional heat flow.
  • the thermal resistance RS of a measurement sample is calculated
  • R S N ((T U ⁇ T L ) / Q) ⁇ R O
  • T U represents a measurement sample top surface temperature
  • T L represents the measurement sample lower surface temperature
  • R O represents the thermal contact resistance of the upper and lower interfaces
  • Q is shows the heat flux meter output.
  • N is a proportionality coefficient, and is obtained in advance using a calibration sample.
  • the compression modulus at 25 ° C. can be 3 MPa or less, but may be 2 MPa or less, 1 MPa or less, or 0.5 MPa or less. Good.
  • the compression elastic modulus is 3 MPa or less, it becomes easy to obtain an airgel composite excellent in handleability.
  • the lower limit value of the compression elastic modulus is not particularly limited, but may be 0.05 MPa, for example.
  • the deformation recovery rate at 25 ° C. can be 90% or more, but may be 94% or more, or 98% or more.
  • the deformation recovery rate is 90% or more, it becomes easier to obtain excellent strength, excellent flexibility for deformation, and the like.
  • the upper limit value of the deformation recovery rate is not particularly limited, but may be, for example, 100% or 99%.
  • the maximum compressive deformation rate at 25 ° C. can be 80% or more, but may be 83% or more, or 86% or more.
  • the upper limit value of the maximum compressive deformation rate is not particularly limited, but may be 90%, for example.
  • the airgel composite is processed into a 7.0 mm square cube (die shape) to obtain a measurement sample.
  • the measurement sample is shaped with a sandpaper of # 1500 or more as necessary.
  • the measurement sample is dried at 100 ° C. for 30 minutes under atmospheric pressure using a constant temperature dryer “DVS402” (manufactured by Yamato Scientific Co., Ltd., product name).
  • the measurement sample is then transferred into a desiccator and cooled to 25 ° C. Thereby, a measurement sample for measuring the compression elastic modulus, deformation recovery rate, and maximum compression deformation rate is obtained.
  • a 500N load cell is used.
  • a stainless upper platen ( ⁇ 20 mm) and a lower platen plate ( ⁇ 118 mm) are used as a compression measurement jig.
  • a measurement sample is set between these jigs, compressed at a speed of 1 mm / min, and the displacement of the measurement sample size at 25 ° C. is measured. The measurement is terminated when a load exceeding 500 N is applied or when the measurement sample is destroyed.
  • the compressive strain ⁇ can be obtained from the following equation.
  • ⁇ ⁇ d / d1
  • ⁇ d represents the displacement (mm) of the thickness of the measurement sample due to the load
  • d1 represents the thickness (mm) of the measurement sample before the load is applied.
  • the compressive stress ⁇ (MPa) can be obtained from the following equation.
  • ⁇ F / A
  • F represents the compressive force (N)
  • A represents the cross-sectional area (mm 2 ) of the measurement sample before applying a load.
  • the compression elastic modulus E (MPa) can be obtained from the following equation in the compression force range of 0.1 to 0.2 N, for example.
  • E ( ⁇ 2 ⁇ 1 ) / ( ⁇ 2 ⁇ 1 )
  • ⁇ 1 indicates a compressive stress (MPa) measured at a compressive force of 0.1 N
  • ⁇ 2 indicates a compressive stress (MPa) measured at a compressive force of 0.2 N
  • ⁇ 1 indicates a compressive stress.
  • the compressive strain measured at ⁇ 1 is shown
  • ⁇ 2 shows the compressive strain measured at the compressive stress ⁇ 2 .
  • thermal conductivity, compression elastic modulus, deformation recovery rate, and maximum compression deformation rate can be appropriately adjusted by changing the production conditions, raw materials, etc. of the airgel composite described later.
  • 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, an airgel composite excellent in flexibility can be easily obtained, and when it is 1000 nm or less, an airgel composite excellent in heat insulation can be easily obtained.
  • the density may be 0.05 ⁇ 0.25g / cm 3 at 25 ° C., or may be 0.1 ⁇ 0.2g / cm 3.
  • the density is 0.05 g / cm 3 or more, more excellent strength and flexibility can be obtained, and when it is 0.25 g / cm 3 or less, more excellent heat insulation can be obtained. it can.
  • the porosity at 25 ° C. can be 85 to 95%, but it may be 87 to 93%.
  • the porosity is 85% or more, more excellent heat insulating properties can be obtained, and when it is 95% or less, more excellent strength and flexibility can be obtained.
  • the average pore diameter, density and porosity of pores (through holes) continuous in a three-dimensional network can be measured by a mercury intrusion method according to DIN 66133.
  • a mercury intrusion method according to DIN 66133.
  • Autopore IV9520 manufactured by Shimadzu Corporation, product name
  • Shimadzu Corporation product name
  • the manufacturing method of an airgel composite is demonstrated.
  • the manufacturing method of an airgel composite is not specifically limited, For example, it can manufacture with the following method.
  • the airgel composite of the present embodiment was obtained in the sol generation step, the wet gel generation step in which the sol obtained in the sol generation step was gelled and then aged to obtain a wet gel, and the wet gel generation step.
  • the wet gel can be produced by a production method mainly comprising a step of washing and (if necessary) replacing the solvent with a solvent and a drying step of drying the wet gel after washing and solvent substitution.
  • the “sol” is a state before the gelation reaction occurs, and in the present embodiment, the silicon compound group, and in some cases, the polysiloxane compound group, and silica particles are dissolved or dispersed in a solvent. Means the state.
  • the wet gel means a gel solid in a wet state that contains a liquid medium but does not have fluidity.
  • generation process is a process which mixes the above-mentioned silicon compound, the polysiloxane compound with the case, and the solvent containing a silica particle and / or a silica particle, and it hydrolyzes and produces
  • an acid catalyst may be further added to the solvent in order to promote the hydrolysis reaction.
  • a surfactant, a thermohydrolyzable compound, or the like can 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 for the purpose of suppressing heat radiation.
  • alcohols for example, water or a mixed solution of water and alcohols can be used.
  • alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, and t-butanol.
  • alcohols having a low surface tension and a low boiling point in terms of reducing the interfacial tension with the gel wall include methanol, ethanol, 2-propanol and the like. You may use these individually or in mixture of 2 or more types.
  • the amount of alcohols can be 4 to 8 mol with respect to 1 mol of the total amount of the silicon compound group and the polysiloxane compound group, but it can be 4 to 6.5. Or 4.5 to 6 moles.
  • the amount of alcohols 4 mol or more it becomes easier to obtain good compatibility, and by making it 8 mol or less, it becomes easier to suppress gel shrinkage.
  • the acid catalyst examples include hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, bromic acid, chloric acid, chlorous acid, hypochlorous acid, and other inorganic acids; acidic phosphoric acid Acidic phosphates such as aluminum, acidic magnesium phosphate and acidic zinc phosphate; organic carboxylic acids such as acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid and azelaic acid Etc. Among these, an organic carboxylic acid is mentioned as an acid catalyst which improves the water resistance of the airgel composite obtained more. Examples of the organic carboxylic acids include acetic acid, but may be formic acid, propionic acid, oxalic acid, malonic acid and the like. You may use these individually or in mixture of 2 or more types.
  • 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 amount of the silicon compound group and the polysiloxane compound group.
  • a nonionic surfactant As the surfactant, a nonionic surfactant, an ionic surfactant, or 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.
  • the compound containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether and the like.
  • the compound having a hydrophilic portion such as polyoxypropylene include polyoxypropylene alkyl ether, a block copolymer of polyoxyethylene and polyoxypropylene, and the like.
  • Examples of the ionic surfactant include a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.
  • Examples of the cationic surfactant include cetyltrimethylammonium bromide and cetyltrimethylammonium chloride, and examples of the anionic surfactant include sodium dodecylsulfonate.
  • Examples of amphoteric surfactants include amino acid surfactants, betaine surfactants, amine oxide surfactants, and the like.
  • Examples of amino acid surfactants include acyl glutamic acid.
  • Examples of betaine surfactants include lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, and the like.
  • Examples of the amine oxide surfactant include lauryl dimethylamine oxide.
  • surfactants have the effect of reducing the difference in chemical affinity between the solvent in the reaction system and the growing siloxane polymer and suppressing phase separation in the wet gel formation process described later. It is considered to be.
  • the addition amount of the surfactant depends on the kind of the surfactant, or the kind and amount of the silicon compound group and the polysiloxane compound group.
  • the total amount of the silicon compound group and the polysiloxane compound group is 100 parts by mass. 1 to 100 parts by mass.
  • the added 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 generation process described later. Accordingly, the thermohydrolyzable compound is not particularly limited as long as it can make the reaction solution basic after hydrolysis.
  • Urea formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N -Acid amides such as methylacetamide and N, N-dimethylacetamide; cyclic nitrogen compounds such as hexamethylenetetramine and the like.
  • urea is particularly easy to obtain the above-mentioned promoting effect.
  • the addition amount of the thermohydrolyzable compound is not particularly limited as long as it can sufficiently promote the sol-gel reaction in the wet gel generation step described later.
  • the amount added can be 1 to 200 parts by mass with respect to 100 parts by mass as the total of the silicon compound group and the polysiloxane compound group.
  • the added amount may be 2 to 150 parts by mass.
  • the hydrolysis in the sol production step depends on the types and amounts of silicon compound, polysiloxane compound, silica particles, acid catalyst, surfactant, etc. in the mixed solution, but for example in a temperature environment of 20 to 60 ° C.
  • the treatment may be performed for 10 minutes to 24 hours, or in a temperature environment of 50 to 60 ° C. for 5 minutes to 8 hours.
  • the temperature environment of the sol generation step may be adjusted to a temperature that suppresses hydrolysis of the thermohydrolyzable compound and suppresses gelation of the sol. .
  • the temperature at this time may be any temperature as long as the hydrolysis of the thermally hydrolyzable compound can be suppressed.
  • the temperature environment of the sol production step can be 0 to 40 ° C., but may be 10 to 30 ° C.
  • the wet gel generation step is a step in which the sol obtained in the sol generation step is gelled and then aged to obtain a wet gel.
  • a base catalyst can be used to promote gelation.
  • Base catalysts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; ammonium compounds such as ammonium hydroxide, ammonium fluoride, ammonium chloride, and ammonium bromide; sodium metaphosphate Basic sodium phosphates such as sodium pyrophosphate and sodium polyphosphate; allylamine, diallylamine, triallylamine, isopropylamine, diisopropylamine, ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3 -(Diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, tetramethylethylenediamine, t-butylamine, sec Aliphatic amines such as butylamine, propylamine, 3- (
  • ammonium hydroxide (ammonia water) is excellent in that it has high volatility and does not easily remain in the airgel composite after drying, so that it is difficult to impair the water resistance, and is economical. You may use said base catalyst individually or in mixture of 2 or more types.
  • the dehydration condensation reaction and / or dealcoholization condensation reaction of the silicon compound group, polysiloxane compound group, and silica particles in the sol can be promoted, and the sol can be gelled in a shorter time. It can be carried out. Thereby, a wet gel with higher strength (rigidity) can be obtained.
  • ammonia has high volatility and hardly remains in the airgel composite. Therefore, by using ammonia as a base catalyst, an airgel composite having better 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 of the total amount 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, gelatinization can be performed in a short time, and a water resistance fall can be suppressed more by setting it as 5 mass part or less.
  • the gelation of the sol in the wet gel generation step may be performed in a sealed container so that the solvent and the base catalyst do not volatilize.
  • the gelation temperature can be 30 to 90 ° C., but it may be 40 to 80 ° C. By setting the gelation temperature to 30 ° C. or higher, gelation can be performed in a shorter time, and a wet gel with higher strength (rigidity) can be obtained. Moreover, since it becomes easy to suppress volatilization of a solvent (especially alcohol) by making gelation temperature into 90 degrees C or less, it can gelatinize, suppressing volume shrinkage.
  • the aging in the wet gel generation step may be performed in a sealed container so that the solvent and the base catalyst do not volatilize.
  • the aging temperature can be 30 to 90 ° C., but it may be 40 to 80 ° C.
  • the aging temperature can be 30 to 90 ° 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 (especially alcohols) can be easily suppressed. Therefore, it can be gelled while suppressing volume shrinkage.
  • gelation of the sol and subsequent aging may be performed in a series of operations.
  • the gelation time and the aging time differ depending on the gelation temperature and the aging temperature, in the present embodiment, since the sol contains silica particles, the gelation time is particularly compared with the conventional method for producing an airgel. Can be shortened. The reason is presumed that the silanol groups and / or reactive groups possessed by the silicon compound, polysiloxane compound, etc. in the sol form hydrogen bonds and / or chemical bonds with the silanol groups of the silica particles.
  • the gelation time can be 10 to 120 minutes, but may be 20 to 90 minutes.
  • the drying process can be simplified from the washing and solvent replacement process described later.
  • the total time of the gelation time and the aging time in the entire gelation and aging process can be 4 to 480 hours, but may be 6 to 120 hours.
  • the gelation temperature and the aging temperature are increased within the above range, or the total time of the gelation time and the aging time is increased within the above range. May be. Further, in order to increase the density of the obtained airgel composite or to reduce the average pore diameter, the gelation temperature and the aging temperature are reduced within the above range, or the total time of the gelation time and the aging time is within the above range. It can be shortened.
  • the washing and solvent replacement step is a step of washing the wet gel obtained by the wet gel generation step (washing step), and a step of replacing the washing liquid in the wet gel with a solvent suitable for the drying conditions (the drying step described later). It is a process which has (solvent substitution process).
  • the washing and solvent replacement step can be performed in a form in which only the solvent replacement step is performed without performing the step of washing the wet gel, but the impurities such as unreacted substances and by-products in the wet gel are reduced, and more From the viewpoint of enabling the production of a highly pure airgel composite, the wet gel may be washed.
  • the solvent replacement step is not necessarily essential as described later.
  • the wet gel obtained in the wet gel production step is washed.
  • the washing can be repeatedly performed using, for example, water or an organic solvent. At this time, washing efficiency can be improved by heating.
  • Organic solvents include 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 , N, N-dimethylformamide, dimethyl sulfoxide, acetic acid, formic acid, and other various organic solvents can be used. You may use said organic solvent individually or in mixture of 2 or more types.
  • a low surface tension solvent can be used in order to suppress gel shrinkage due to drying.
  • low surface tension solvents generally have very low mutual solubility with water. Therefore, when using a low surface tension solvent in the solvent replacement step, examples of the organic solvent used in the washing step include hydrophilic organic solvents having high mutual solubility in both water and a low surface tension solvent. Note that the hydrophilic organic solvent used in the washing step can serve as a preliminary replacement for the solvent replacement step.
  • examples of hydrophilic organic solvents include methanol, ethanol, 2-propanol, acetone, and methyl ethyl ketone. Methanol, ethanol, methyl ethyl ketone and the like are excellent in terms of economy.
  • the amount of water or organic solvent used in the washing step can be an amount that can be sufficiently washed by replacing the solvent in the wet gel.
  • the amount can be 3 to 10 times the volume of the wet gel.
  • the washing can be repeated until the moisture content in the wet gel after washing is 10% by mass or less with respect to the silica mass.
  • the temperature environment in the washing step can be a temperature not higher than the boiling point of the solvent used for washing.
  • the temperature can be raised to about 30 to 60 ° C.
  • 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 replacement efficiency can be improved by heating.
  • Specific examples of the solvent for substitution include a low surface tension solvent described later in the drying step when drying is performed under atmospheric pressure at a temperature lower 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 a mixture of two or more thereof.
  • Examples of the low surface tension solvent include a solvent having a surface tension at 20 ° C. of 30 mN / m or less. The surface tension may be 25 mN / m or less, or 20 mN / m or less.
  • Examples of the low surface tension solvent include pentane (15.5), hexane (18.4), heptane (20.2), octane (21.7), 2-methylpentane (17.4), 3- Aliphatic hydrocarbons such as methylpentane (18.1), 2-methylhexane (19.3), cyclopentane (22.6), cyclohexane (25.2), 1-pentene (16.0); Aromatic hydrocarbons such as (28.9), toluene (28.5), m-xylene (28.7), p-xylene (28.3); dichloromethane (27.9), chloroform (27.2) ), Carbon tetrachloride (26.9), 1-chloropropane (21.8),
  • aliphatic hydrocarbons hexane, heptane, etc.
  • a hydrophilic organic solvent such as acetone, methyl ethyl ketone, 1,2-dimethoxyethane
  • it can be used as the organic solvent in the washing step.
  • a solvent having a boiling point of 100 ° C. or less at normal pressure may be used because it is easy to dry in the drying step described later. You may use said solvent individually or in mixture of 2 or more types.
  • the amount of the 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 not higher than the boiling point of the solvent used for the replacement.
  • the temperature can be increased to about 30 to 60 ° C.
  • the solvent replacement step is not necessarily essential as described above.
  • the inferred mechanism is as follows. That is, conventionally, in order to suppress shrinkage in the drying process, the solvent of the wet gel is replaced with a predetermined replacement solvent (a low surface tension solvent), but in this embodiment, the silica particles are in a three-dimensional network shape. By functioning as a skeleton support, the skeleton 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 washing. Thus, in this embodiment, the drying process can be simplified from the washing and solvent replacement process. However, this embodiment does not exclude performing the solvent substitution step at all.
  • the drying method is not particularly limited, and known atmospheric pressure drying, supercritical drying, or freeze drying can be used.
  • atmospheric drying or supercritical drying can be used from the viewpoint of easy production of a low-density airgel composite.
  • atmospheric pressure drying can be used.
  • the normal pressure means 0.1 MPa (atmospheric pressure).
  • the airgel composite of the present embodiment can be obtained by drying a wet gel that has been washed and solvent-substituted (if necessary) at a temperature below the critical point of the solvent used for drying under atmospheric pressure.
  • the drying temperature varies depending on the type of substituted solvent (the solvent used for washing if solvent substitution is not performed), but especially when drying at a high temperature increases the evaporation rate of the solvent and causes large cracks in the gel. In view of the fact that the temperature is 20 to 150 ° C.
  • the drying temperature may be 60 to 120 ° C.
  • the drying time varies depending on the wet gel volume and the drying temperature, but can be 4 to 120 hours. In the present embodiment, it is also included in the atmospheric pressure drying to accelerate the drying by applying a pressure less than the critical point within a range not inhibiting the productivity.
  • the airgel composite of the present embodiment can also be obtained by supercritical drying a wet gel that has been washed and (if necessary) solvent-substituted.
  • Supercritical drying can be performed by a known method. Examples of the supercritical drying method include a method of removing the solvent at a temperature and pressure higher than the critical point of the solvent contained in the wet gel.
  • all or part of the solvent contained in the wet gel is obtained by immersing the wet gel in liquefied carbon dioxide, for example, at about 20 to 25 ° C. and about 5 to 20 MPa. And carbon dioxide having a lower critical point than that of the solvent, and then removing carbon dioxide alone or a mixture of carbon dioxide and the solvent.
  • the airgel composite obtained by such normal pressure drying or supercritical drying may be further dried at 105 to 200 ° C. for about 0.5 to 2 hours under normal pressure. This makes it easier to obtain an airgel composite having a low density and having small pores. Additional drying may be performed at 150 to 200 ° C. under normal pressure.
  • the support member with an airgel composite of the present embodiment includes the airgel composite described so far and a support member that supports the airgel composite.
  • Such a support member with an airgel composite can exhibit high heat insulation and excellent flexibility.
  • the support member examples include a film-like support member, a sheet-like support member, a foil-like support member, and a porous support member.
  • the film-like support member is a member obtained by forming a polymer raw material into a thin film, and examples thereof include organic films such as PET and polyimide, glass films, and the like (including metal vapor deposited films).
  • the sheet-like support member is a member obtained by molding an organic, inorganic, and / or metal fiber raw material, and examples thereof include paper, nonwoven fabric (including glass mat), organic fiber cloth, and glass cloth.
  • the foil-like support member is a member obtained by forming a metal raw material into a thin film, and examples thereof include aluminum foil and copper foil.
  • the porous support member is a member having a porous structure made of organic, inorganic and / or metal as a raw material, and is made of a porous organic material (for example, polyurethane foam), a porous inorganic material (for example, zeolite sheet), or porous. Examples thereof include metal materials (for example, porous metal sheets and porous aluminum sheets).
  • the support member with the airgel composite can be produced, for example, as follows. First, a sol is prepared according to the sol generation process described above. After applying the sol onto the support member using a film applicator or the like, or impregnating the sol with the support member, a support member with a wet gel is obtained according to the above-described wet gel generating step. And the support member with an airgel composite is obtained by performing washing
  • the thickness of the airgel composite formed on the film-like support member or the foil-like support member can be 1 to 200 ⁇ m, but may be 10 to 100 ⁇ m, or 30 to 80 ⁇ m. When the thickness is 1 ⁇ m or more, it is easy to obtain good heat insulating properties, and when it is 200 ⁇ m or less, flexibility is easily obtained.
  • the airgel composite of the present embodiment described as described above has excellent heat insulating properties and flexibility, which has been difficult to achieve with conventional airgel, by containing an airgel component and silica particles.
  • the particularly excellent flexibility made it possible to form an airgel composite layer on a film-like support member and a foil-like support member, which had been difficult to achieve in the past. Therefore, the support member with an airgel composite of the present embodiment has high heat insulating properties and excellent flexibility.
  • the support member with an airgel composite of the present embodiment has high heat insulating properties and excellent flexibility.
  • the airgel composite and the support member with the airgel composite of the present embodiment can be applied to a use as a heat insulating material in an architectural field, an automobile field, a home appliance, a semiconductor field, an industrial facility, and the like.
  • the airgel composite of this embodiment can be used as a coating additive, cosmetics, antiblocking agent, catalyst carrier, etc., in addition to its use as a heat insulating material.
  • the heat insulating material of the present embodiment includes the airgel composite described so far, and has high heat insulating properties and excellent flexibility.
  • the airgel composite obtained by the manufacturing method of the said airgel composite can be made into a heat insulating material as it is (processed into a predetermined shape as needed).
  • Example 1 [wet gel, airgel composite] 60.0 parts by mass of methyltrimethoxysilane LS-530 (manufactured by Shin-Etsu Chemical Co., Ltd., product name: hereinafter abbreviated as “MTMS”) and dimethyldimethoxysilane LS-520 (manufactured by Shin-Etsu Chemical Co., Ltd., product) Name: 40.0 parts by mass of “DMDMS”) and PL-2L as a silica particle-containing raw material (details of PL-2L are described in Table 1. The same applies to the silica particle-containing raw material).
  • MTMS methyltrimethoxysilane LS-530
  • MTMS dimethyldimethoxysilane LS-520
  • sol 1 0 parts by mass, 40.0 parts by mass of water and 80.0 parts by mass of methanol were mixed, and 0.10 parts by mass of acetic acid as an acid catalyst was added thereto, and reacted at 25 ° C. for 2 hours to obtain sol 1.
  • the obtained wet gel 1 was immersed in 2500.0 parts by mass of methanol and washed at 60 ° C. for 12 hours. This washing operation was performed 3 times while exchanging with fresh methanol.
  • the washed wet gel was immersed in 2500.0 parts by mass of heptane, which is a low surface tension solvent, and solvent substitution was performed at 60 ° C. for 12 hours. This solvent replacement operation was performed three times while exchanging with new heptane.
  • the washed and solvent-substituted wet gel is dried under normal pressure at 40 ° C. for 96 hours, and then further dried at 150 ° C. for 2 hours, whereby the structures represented by the above general formulas (4) and (5) The airgel composite 1 which has this was obtained.
  • [Support member with airgel composite] A film-like support member with an airgel composite
  • the sol 1 is formed into a film made of polyethylene terephthalate (longitudinal) 300 mm ⁇ (horizontal) 270 mm ⁇ (thickness) 12 ⁇ m so that the thickness after gelation is 40 ⁇ m (tester) PI-1210) manufactured by Sangyo Co., Ltd. was applied, gelled at 60 ° C. for 3 hours, and then aged at 80 ° C. for 24 hours to obtain a film-like support member 1 with a wet gel.
  • the obtained film-like support member 1 with wet gel was immersed in 100 mL of methanol and washed at 60 ° C. for 2 hours.
  • the washed film-like support member with wet gel was immersed in 100 mL of methyl ethyl ketone, and the solvent was replaced at 60 ° C. for 2 hours. This solvent replacement operation was performed twice while exchanging with new methyl ethyl ketone.
  • the washed and solvent-substituted film-like support member with a wet gel was dried at 120 ° C. for 6 hours under normal pressure to obtain a film-like support member 1 with an airgel composite.
  • the sol 1 is placed in an E glass cloth of (length) 300 mm x (width) 270 mm x (thickness) 100 ⁇ m so that the thickness of the sheet-like support member after gelation is 120 ⁇ m. After impregnation and gelation at 60 ° C. for 3 hours, aging at 80 ° C. for 24 hours yielded a sheet-like support member 1 with a wet gel.
  • the obtained sheet-like support member 1 with wet gel was immersed in 300 mL of methanol and washed at 60 ° C. for 2 hours.
  • the washed sheet-like support member with wet gel was immersed in 300 mL of methyl ethyl ketone, and the solvent was replaced at 60 ° C. for 2 hours. This solvent replacement operation was performed twice while exchanging with new methyl ethyl ketone.
  • the washed and solvent-substituted sheet-like support member with a wet gel was dried at 120 ° C. for 8 hours under normal pressure to obtain a sheet-like support member 1 with an airgel composite.
  • the sol 1 is applied to a (longitudinal) 300 mm x (horizontal) 270 mm x (thickness) 12 ⁇ m aluminum foil using a film applicator so that the thickness after gelation is 40 ⁇ m. Then, after gelling at 60 ° C. for 3 hours, it was aged at 80 ° C. for 24 hours to obtain a foil-like support member 1 with a wet gel.
  • the obtained foil-like support member 1 with wet gel was immersed in 100 mL of methanol and washed at 60 ° C. for 2 hours.
  • the washed foil-like support member with wet gel was immersed in 100 mL of methyl ethyl ketone, and solvent substitution was performed at 60 ° C. for 2 hours. This solvent replacement operation was performed twice while exchanging with new methyl ethyl ketone.
  • the washed and solvent-substituted foil-like support member with a wet gel was dried at 120 ° C. for 6 hours under normal pressure to obtain a foil-like support member 1 with an airgel composite.
  • the above sol 1 is made into a flexible urethane foam of (length) 300 mm x (width) 270 mm x (thickness) 10 mm so that the thickness of the porous support member after gelation becomes 10 mm. After impregnating and gelling at 60 ° C. for 3 hours, it was aged at 80 ° C. for 24 hours to obtain a porous support member 1 with wet gel.
  • porous support member 1 with wet gel was immersed in 300 mL of methanol and washed at 60 ° C. for 2 hours.
  • the washed porous support member with wet gel was immersed in 300 mL of methyl ethyl ketone, and the solvent was replaced at 60 ° C. for 2 hours. This solvent replacement operation was performed twice while exchanging with new methyl ethyl ketone.
  • the porous support member 1 with an airgel composite was obtained by drying the washed and solvent-substituted porous support member with a wet gel at 120 ° C. for 10 hours under normal pressure.
  • Example 2 [Wet gel, airgel composite] 100.0 parts by mass of PL-2L as a silica particle-containing raw material, 100.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, cetyltrimethylammonium bromide as a cationic surfactant (Wako Pure Chemical Industries, Ltd.) Co., Ltd. (hereinafter abbreviated as “CTAB”) was mixed with 20.0 parts by mass of urea and 120.0 parts by mass of urea as a thermally hydrolyzable compound, and then 70.0 parts by mass of MTMS and 30 parts of DMDMS as silicon compounds. 0.0 part by mass was added and reacted at 25 ° C. for 2 hours to obtain sol 2.
  • CTAB cetyltrimethylammonium bromide
  • the obtained sol 2 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 2. Then, the airgel composite 2 which has the structure represented by the said General formula (4) and (5) was obtained like Example 1 using the obtained wet gel 2.
  • FIG. 1 The obtained sol 2 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 2. Then, the airgel composite 2 which has the structure represented by the said General formula (4) and (5) was obtained like Example 1 using the obtained wet gel 2.
  • Example 3 [wet gel, airgel composite] 200.0 parts by mass of PL-5 as a silica particle-containing raw material, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120. urea as a thermohydrolyzable compound. 0 parts by mass was mixed, and 60.0 parts by mass of MTMS and 40.0 parts by mass of DMDMS were added as silicon compounds to this, and reacted at 25 ° C. for 2 hours to obtain sol 3. The obtained sol 3 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 3. Then, the airgel composite 3 which has the structure represented by the said General formula (4) and (5) was obtained like Example 1 using the obtained wet gel 3.
  • Example 4 [wet gel, airgel composite] 100.0 parts by mass of PL-2L as a raw material containing silica particles, 100.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and hot water addition 120.0 parts by mass of urea is mixed as a decomposable compound, 60.0 parts by mass of MTMS and 20.0 parts by mass of DMDMS as a silicon compound, and 20.0 parts by mass of polysiloxane compound A as a polysiloxane compound.
  • sol 4 was obtained by reacting at 25 ° C. for 2 hours. The obtained sol 4 was gelled at 60 ° C.
  • 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 hydroxy-terminated dimethylpolysiloxane “XC96-723” (product name, manufactured by Momentive), 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, this reaction solution was heated at 140 ° C. for 2 hours under reduced pressure of 1.3 kPa to remove volatile components, thereby obtaining a bifunctional alkoxy-modified polysiloxane compound (polysiloxane compound A) at both ends.
  • Example 5 [wet gel, airgel composite]
  • a silica particle-containing raw material 100.0 parts by mass of HL-3L, 100.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and thermal hydrolysis 120.0 parts by mass of urea is mixed as a decomposable compound, 60.0 parts by mass of MTMS and 20.0 parts by mass of DMDMS as a silicon compound, and 20.0 parts by mass of polysiloxane compound A as a polysiloxane compound.
  • sol 5 was obtained by reacting at 25 ° C. for 2 hours.
  • the obtained sol 5 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 5.
  • the airgel composite 5 which has the structure represented by the said General formula (3), (4) and (5) was obtained like Example 1 using the obtained wet gel 5.
  • Example 6 [wet gel, airgel composite] 143.0 parts by mass of ST-OZL-35 as a raw material containing silica particles, 57.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, 120.0 parts by mass of urea was mixed as a thermally hydrolyzable compound, 60.0 parts by mass of MTMS and 20.0 parts by mass of DMDMS as silicon compounds, and 20.0 parts of polysiloxane compound B as a polysiloxane compound. A mass part was added and reacted at 25 ° C. for 2 hours to obtain sol 6. The obtained sol 6 was gelled at 60 ° C.
  • the “polysiloxane compound B” 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 XC96-723, 202.6 parts by mass of tetramethoxysilane and 0. 50 parts by mass was mixed and reacted at 30 ° C. for 5 hours. Thereafter, this 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 trifunctional alkoxy-modified polysiloxane compound (polysiloxane compound B) at both ends.
  • Comparative Example 1 [wet gel, aerogel] 200.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed. 100.0 parts by mass of MTMS as a silicon compound was added and reacted at 25 ° C. for 2 hours to obtain Sol 1C. The obtained sol 1C was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 1C. Thereafter, an airgel 1C was obtained in the same manner as in Example 1 by using the obtained wet gel 1C.
  • Example 2 200.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed.
  • As a silicon compound 80.0 parts by mass of MTMS and 20.0 parts by mass of DMDMS were added and reacted at 25 ° C. for 2 hours to obtain sol 2C.
  • the obtained sol 2C was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 2C. Thereafter, an airgel 2C was obtained in the same manner as in Example 1 using the obtained wet gel 2C.
  • Example 4 200.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed.
  • As a silicon compound 60.0 parts by mass of MTMS and 40.0 parts by mass of DMDMS were added and reacted at 25 ° C. for 2 hours to obtain sol 4C.
  • the obtained sol 4C was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 4C. Thereafter, a comparative airgel 4C was obtained in the same manner as in Example 1 by using the obtained wet gel 4C.
  • Table 1 summarizes the modes of the silica particle-containing raw materials in each example.
  • Table 2 summarizes the drying method, the types and addition amounts of Si raw materials (silicon compounds and polysiloxane compounds), and the addition amounts of silica particle-containing raw materials in each Example and Comparative Example.
  • the wet gel, airgel composite and support member with airgel composite obtained in each example, and the wet gel, airgel and support member with airgel obtained in each comparative example were measured or evaluated according to the following conditions.
  • Summary of gelation time in wet gel formation process, airgel composite and airgel state in atmospheric pressure drying of methanol-substituted gel, and evaluation results of thermal conductivity, compressive elastic modulus, density and porosity of airgel composite and airgel Table 3 summarizes the evaluation results of the 180 ° bending test of the support member with the airgel composite and the support member with the airgel.
  • the volume shrinkage ratio SV before and after drying of the sample was obtained from the following equation.
  • the volume shrinkage ratio SV was 5% or less, it was evaluated as “no contraction”, and when it was 5% or more, it was evaluated as “shrinkage”.
  • SV (V 0 ⁇ V 1 ) / V 0 ⁇ 100
  • V 0 represents the volume of the sample before drying
  • V 1 represents the volume of the sample after drying.
  • the thermal conductivity was measured using a steady-state thermal conductivity measuring device “HFM436 Lambda” (manufactured by NETZSCH, product name).
  • the measurement conditions were an average temperature of 25 ° C. under atmospheric pressure.
  • the measurement sample obtained as described above was sandwiched between the upper and lower heaters with a load of 0.3 MPa, the temperature difference ⁇ T was set to 20 ° C., and the guard sample was adjusted so as to obtain a one-dimensional heat flow. Upper surface temperature, lower surface temperature, etc. were measured.
  • thermal resistance RS of the measurement sample was calculated
  • R S N ((T U ⁇ T L ) / Q) ⁇ R O
  • T U represents a measurement sample top surface temperature
  • T L represents the measurement sample lower surface temperature
  • R O represents the thermal contact resistance of the upper and lower interfaces
  • Q is shows the heat flux meter output.
  • N is a proportionality coefficient, and is obtained in advance using a calibration sample.
  • a small tabletop testing machine “EZTest” manufactured by Shimadzu Corporation, product name
  • 500N was used as a load cell.
  • an upper platen ( ⁇ 20 mm) and a lower platen ( ⁇ 118 mm) made of stainless steel were used as compression measurement jigs.
  • a measurement sample was set between an upper platen and a lower platen arranged in parallel, and compression was performed at a speed of 1 mm / min.
  • the measurement temperature was 25 ° C., and the measurement was terminated when a load exceeding 500 N was applied or when the measurement sample was destroyed.
  • the strain ⁇ was obtained from the following equation.
  • ⁇ ⁇ d / d1
  • ⁇ d the displacement (mm) of the thickness of the measurement sample due to the load
  • d1 the thickness (mm) of the measurement sample before the load is applied.
  • the compressive stress ⁇ (MPa) was obtained from the following equation.
  • ⁇ F / A
  • F represents the compressive force (N)
  • A represents the cross-sectional area (mm 2 ) of the measurement sample before applying a load.
  • the compressive elastic modulus E (MPa) was obtained from the following equation in the compression force range of 0.1 to 0.2N.
  • E ( ⁇ 2 ⁇ 1 ) / ( ⁇ 2 ⁇ 1 )
  • ⁇ 1 indicates a compressive stress (MPa) measured at a compressive force of 0.1 N
  • ⁇ 2 indicates a compressive stress (MPa) measured at a compressive force of 0.2 N
  • ⁇ 1 indicates a compressive stress.
  • the compressive strain measured at ⁇ 1 is shown
  • ⁇ 2 shows the compressive strain measured at the compressive stress ⁇ 2 .
  • the airgel composites of the examples had a short gelation time in the wet gel production process and excellent reactivity, and had good shrinkage resistance in atmospheric drying using a methanol-substituted gel.
  • good shrinkage resistance was shown in any of the examples, that is, a good-quality airgel composite could be obtained without performing the solvent replacement step. .
  • the airgel composites of the examples have small thermal conductivity and compression modulus, and are excellent in both high heat insulation and high flexibility. Moreover, the support member with an airgel composite of the example had good bending resistance.
  • FIG. 3 shows the surface of the airgel composite in the foil-like support member with the airgel composite obtained in Example 4, (a) 10,000 times, (b) 50,000 times, (c) 200,000 times and (d ) SEM images observed at 350,000 times.
  • FIG. 4 shows the surface of the airgel composite in the foil-like support member with the airgel composite obtained in Example 6, with (a) 10,000 times, (b) 50,000 times, and (c) 200,000 times, respectively. It is the observed SEM image.
  • the airgel composite obtained in Example 4 had a three-dimensional network skeleton (three-dimensionally fine porous structure).
  • the observed particle size was mainly about 20 nm derived from silica particles.
  • Spherical airgel components (aerogel particles) with a particle diameter smaller than that of the silica particles can also be confirmed, but mainly the airgel components do not take a spherical form and cover the silica particles or function as a binder between the silica particles. Observed to be. Thus, since a part of airgel component functions as a binder between silica particles, it is guessed that the intensity
  • the airgel composite obtained in Example 6 also has a three-dimensional network skeleton.
  • the cluster structure is unique.
  • the structure is such that particles and particles are connected in a bead shape unlike ordinary airgel, and the connection part of particles and particles seems to be packed densely with an airgel component (silicone component). It is observed that there is.
  • grains derived from a silica particle is significantly larger than the particle diameter of the silica particle itself, it is guessed that the silica particle is coat
  • the airgel component not only functions as a binder between particles, but also covers the entire cluster structure, so it is assumed that the strength of the airgel composite can be further improved. Is done.
  • Example 6 since ST-OZL-35 used was an acidic sol, an airgel composite was produced with a low pH in the system. Therefore, it is guessed that the production

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Abstract

La présente invention concerne un composite d'aérogel qui est le produit séché d'un gel humide qui est un condensat d'un sol contenant des particules de silice, qui ont 10×1018 à 1000×1018 groupes silanol par gramme, et au moins une substance choisie dans le groupe constitué de : composés de silicium ayant un groupe fonctionnel hydrolysable ou un groupe fonctionnel condensable ; et des hydrolysats de composés de silicium comportant ledit groupe fonctionnel hydrolysable.
PCT/JP2016/075226 2015-09-01 2016-08-29 Composite d'aérogel, matériau de support avec aérogel composite, et matériau thermo-isolant Ceased WO2017038777A1 (fr)

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US12325639B2 (en) 2019-03-06 2025-06-10 Fuso Chemical Co., Ltd. Colloidal silica and production method therefor
US12378126B2 (en) 2019-03-06 2025-08-05 Fuso Chemical Co., Ltd. Colloidal silica, and method for production thereof
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