WO2016047740A1 - エアロゲル複合体、エアロゲル複合体付き支持部材及び断熱材 - Google Patents
エアロゲル複合体、エアロゲル複合体付き支持部材及び断熱材 Download PDFInfo
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- WO2016047740A1 WO2016047740A1 PCT/JP2015/077060 JP2015077060W WO2016047740A1 WO 2016047740 A1 WO2016047740 A1 WO 2016047740A1 JP 2015077060 W JP2015077060 W JP 2015077060W WO 2016047740 A1 WO2016047740 A1 WO 2016047740A1
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- WIPO (PCT)
- Prior art keywords
- airgel
- airgel composite
- mass
- support member
- parts
- Prior art date
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Images
Classifications
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- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
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- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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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
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- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C01B33/157—After-treatment of gels
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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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G77/04—Polysiloxanes
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- 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
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- E—FIXED CONSTRUCTIONS
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- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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 invention 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.
- a technique for drying alcogel using a general-purpose method that does not require a high-pressure process has been proposed.
- a method of improving the strength of the resulting alcogel by using a monoalkyltrialkoxysilane and a tetraalkoxysilane in combination at a specific ratio as a gel material and drying at normal pressure is known.
- the gel tends to contract due to stress caused by the capillary force inside the alcogel.
- 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.
- This invention is made
- the present invention also provides a support member with an airgel composite formed by supporting such an airgel composite, and a heat insulating material.
- an airgel composite in which silica particles are composited in an airgel exhibits excellent heat insulation and flexibility. It was.
- the present invention provides an airgel composite containing an airgel component and silica particles. Unlike the airgel obtained by the prior art, the airgel composite of the present invention is excellent in heat insulation and flexibility.
- the airgel composite can have a three-dimensional network skeleton formed from an airgel component and silica particles, and pores. Thereby, it becomes easy to improve heat insulation and a softness
- the present invention also provides an airgel composite containing silica particles as a component constituting a three-dimensional network skeleton.
- the airgel composite thus obtained is excellent in heat insulation and flexibility.
- the present invention is also produced from a sol containing silica particles and at least one selected from the group consisting of a silicon compound having a hydrolyzable functional group in the molecule and a hydrolysis product of the silicon compound.
- An airgel composite obtained by drying a wet gel is provided.
- the airgel composite thus obtained is excellent in heat insulation and flexibility.
- the airgel composite described above also contains silica particles and at least one selected from the group consisting of a silicon compound having a hydrolyzable functional group in the molecule and a hydrolysis product of the silicon compound.
- a wet gel produced from a sol may be dried.
- the sol may further contain at least one selected from the group consisting of a polysiloxane compound having a reactive group in the molecule and a hydrolysis product of the polysiloxane compound.
- the sol may further contain at least one selected from the group consisting of a polysiloxane compound having a reactive group in the molecule and a hydrolysis product of the polysiloxane compound.
- 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 may be spherical.
- the silica particles can be amorphous silica particles, and the amorphous silica particles can be at least one selected from the group consisting of fused silica particles, fumed silica particles, and colloidal silica particles. . Thereby, further excellent heat insulation and flexibility can be achieved.
- the said drying can be performed under the temperature and atmospheric pressure below the critical point of the solvent used for drying. This makes it easier to obtain an airgel composite that is excellent in heat insulation and flexibility.
- the present invention further provides a support member with an airgel composite comprising the above airgel composite and a support member supporting the airgel composite.
- the said airgel composite has the outstanding heat insulation and a softness
- the present invention further provides a heat insulating material provided with the airgel composite.
- the heat insulating material according to the present invention 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. it can.
- 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.
- a support member with an airgel composite formed by supporting such an airgel composite and a heat insulating material can be provided.
- the important point according to the present invention is that it becomes easier to control the heat insulation and flexibility than the conventional airgel. 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 15 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.
- the obtained low-density dried gel is referred to as an 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 the airgel has a network-like fine structure, and has a cluster structure in which airgel particles of about 2 to 20 nm are combined. Between the skeletons formed by the clusters, there are pores less than 100 nm, and a three-dimensionally fine porous structure is formed.
- the airgel in this embodiment is a silica airgel which has a silica as a main component. Examples of 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 for example, an embodiment in which silica particles are coated with a film-like airgel component (silicone) (an embodiment in which the airgel component includes 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), 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, but the present invention is not limited to the embodiment of FIG. 1 as described above.
- the following descriptions can be referred to as appropriate.
- FIG. 1 is a diagram schematically showing the fine structure of an airgel composite according to an embodiment of the present invention.
- the airgel composite 10 includes a three-dimensional network skeleton formed by three-dimensionally connecting airgel particles 1 that are airgel components in random three-dimensionally via silica particles 2, and And pores 3 surrounded by a 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 silicone, 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 average particle size (that is, the secondary particle size) of the airgel particles 1 can be 2 nm to 50 ⁇ m, but may be 5 nm to 2 ⁇ m, or may be 10 nm to 200 nm.
- the airgel particle 1 has an average particle diameter of 2 nm or more, an airgel composite having excellent flexibility can be easily obtained.
- the average particle diameter is 50 ⁇ m or less, an airgel composite having excellent heat insulation can be easily obtained. Become.
- 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 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 spherical, eyebrows, and association types. 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 to 500 nm, but may be 5 to 300 nm, or 20 to 100 nm. When the average primary particle diameter of the silica particles 2 is 1 nm or more, it becomes easy to impart an appropriate strength to the airgel, and an airgel composite having excellent shrinkage resistance during drying is easily obtained. On the other hand, when 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 particles 1 (aerogel component) and the silica particles 2 are bonded in a hydrogen bond, chemical bond, or a combination of these bonds.
- hydrogen bonds, chemical bonds, or combinations of these bonds are considered to be formed by the silanol groups, reactive groups, or both 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 can be 10 ⁇ 10 18 to 1000 ⁇ 10 18 pcs / g, but may be 50 ⁇ 10 18 to 800 ⁇ 10 18 pcs / g, It may be 10 18 to 700 ⁇ 10 18 pieces / g.
- 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 average particle size of the particles is measured using a scanning electron microscope (hereinafter abbreviated as “SEM”). It can be obtained by directly observing the cross section of.
- 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, taking colloidal silica particles having a solid content concentration of 5 to 40% by mass normally dispersed in water as an example, a chip obtained by cutting a wafer with a patterned wiring into 2 cm squares for about 30 seconds in a dispersion of colloidal silica particles. After soaking, 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 to 25 parts by mass with respect to 100 parts by mass of the total amount of the airgel composite, but may be 10 to 20 parts by mass.
- 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 silica particles contained in the airgel composite can be 1 to 25 parts by mass with respect to 100 parts by mass of the total amount of the airgel composite, but may be 3 to 15 parts by mass.
- 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 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. 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 measurement method of the thermal conductivity using the steady method thermal conductivity measuring device 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 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.
- 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. .
- the compression elastic modulus is 3 MPa or less, it becomes easy to obtain an airgel composite having excellent 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 compression deformation rate is not particularly limited, but can be 90%, for example.
- compression elastic modulus, deformation recovery rate, and maximum compression deformation rate can be measured using a small desktop tester “EZTest” (manufactured by Shimadzu Corporation, product name).
- the outline of the measurement method such as compression modulus using a small tabletop testing machine is as follows.
- 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 compressive elastic modulus E (MPa) can be obtained from the following equation within a 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 airgel composite of this embodiment can have a structure represented by the following general formula (1).
- R 1 and R 2 each independently represent an alkyl group or an aryl group
- R 3 and R 4 each independently represent an alkylene group.
- examples of the aryl group include a phenyl group and a substituted phenyl group.
- a substituent of a substituted phenyl group an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, a cyano group etc. are mentioned, for example.
- R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like, and the alkyl group is a methyl group and the like.
- 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.
- the airgel composite of the present embodiment is an airgel composite having a ladder structure including a support 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). It may be.
- 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 6 and R 7 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.
- a substituent of a substituted phenyl group an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, a cyano group etc. are mentioned, for example.
- b is an integer of 2 or more
- two or more R 6 s may be the same or different, and similarly two or more R 7 s are each the same. May be different.
- the above structure as an airgel component into the skeleton of the airgel complex, for example, it has a structure derived from a conventional ladder-type silsesquioxane (that is, a structure represented by the following general formula (X)
- An airgel composite having flexibility superior to that of the airgel.
- the structure of the bridge portion is —O—, but the airgel composite of this embodiment
- the structure of the bridging portion is a structure (polysiloxane structure) represented by the general formula (2).
- R represents a hydroxy group, an alkyl group or an aryl group.
- the ladder structure has the following general formula (You may have the 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.
- a substituent of a substituted phenyl group an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, a cyano group etc. are mentioned, for example.
- R 5 , R 6 , R 7 and R 8 (however, R 5 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 includes at least one selected from the group consisting of silica particles, a silicon compound having a hydrolyzable functional group in the molecule, and a hydrolysis product of the silicon compound (hereinafter, these silicons).
- a compound obtained by drying a wet gel generated from a sol containing a compound or the like may be collectively referred to as “silicon compounds”).
- the airgel composite described so far may also be obtained by drying a wet gel generated from a sol containing silica particles and silicon compounds.
- the number of silicon atoms in the molecule of the silicon compound can be 1 or 2. Although it does not specifically limit as a silicon compound which has a hydrolyzable functional group in a molecule
- numerator For example, an alkyl silicon alkoxide is mentioned. Alkyl silicon alkoxides can have a hydrolyzable functional group number of 3 or less from the viewpoint of improving water resistance. Specifically, for example, methyltrimethoxysilane, dimethyldimethoxysilane, and ethyltrimethoxy Examples include silane.
- examples of the hydrolyzable functional group include alkoxy groups such as a methoxy group and an ethoxy group.
- the number of hydrolyzable functional groups is 3 or less, and vinyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl which are silicon compounds having a reactive group in the molecule.
- Methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, N- Phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like can also be used.
- bistrimethoxysilylmethane bistrimethoxysilylethane, bistrimethoxysilylhexane, etc., which are silicon compounds having 3 or less hydrolyzable functional groups at the molecular ends can also be used.
- silicon compounds may be used alone or in combination of two or more.
- the sol containing the silicon compounds is selected from the group consisting of a polysiloxane compound having a reactive group in the molecule and a hydrolysis product of the polysiloxane compound.
- these polysiloxane compounds and the like may be collectively referred to as “polysiloxane compounds”).
- the reactive group in the polysiloxane compounds is not particularly limited, but may be a group that reacts with the same reactive group or a group that reacts with another reactive group, for example, an alkoxy group, a silanol group, a hydroxy group. Examples thereof include an alkyl group, an epoxy group, a polyether group, a mercapto group, a carboxyl group, and a phenol group. You may use the polysiloxane compound which has these reactive groups individually or in mixture of 2 or more types. Examples of the reactive group include an alkoxy group, a silanol group, a hydroxyalkyl group, and a polyether group from the viewpoint of improving the flexibility of the airgel composite.
- the alkoxy group or the hydroxyalkyl group is a sol.
- the compatibility can be further improved.
- 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 in the molecule include those having a structure represented by the following general formula (4).
- the structure represented by the general formula (1) can be introduced into the skeleton of the airgel composite.
- R 9 represents a hydroxyalkyl group
- R 10 represents an alkylene group
- R 11 and R 12 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.
- a substituent of a substituted phenyl group an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, a cyano group etc. are mentioned, for example.
- two R 9 s may be the same or different from each other, and similarly two R 10 s may be the same or different from each other.
- two or more R 11 s may be the same or different, and similarly two or more R 12 s may be the same or different.
- R 9 includes a hydroxyalkyl group having 1 to 6 carbon atoms, and the hydroxyalkyl group includes a hydroxyethyl group, a hydroxypropyl group, and the like.
- R 10 includes an alkylene group having 1 to 6 carbon atoms, and examples of the alkylene group include an ethylene group and a propylene group.
- R 11 and R 12 are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group or the like, and the alkyl group is a methyl group or the like.
- n can be 2 to 30, but may be 5 to 20.
- polysiloxane compound having the structure represented by the general formula (4) commercially available products 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 in the molecule include those having a structure represented by the following general formula (5).
- a ladder structure having a bridge portion represented by the general formula (2) is introduced into the skeleton of the airgel composite. be able to.
- R 14 represents an alkyl group or an alkoxy group
- R 15 and R 16 each independently represent an alkoxy group
- R 17 and R 18 each independently represent an alkyl group or an aryl group
- m is An integer from 1 to 50 is shown.
- examples of the aryl group include a phenyl group and a substituted phenyl group.
- a substituent of a substituted phenyl group an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, a cyano group etc. are mentioned, for example.
- two R 14 s may be the same or different
- two R 15 s may be the same or different.
- two R 14 Each 16 may be the same or different.
- when m is an integer of 2 or more
- two or more R 17 s may be the same or different
- similarly two or more R 18 are each the same. May be different.
- examples of R 14 include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.
- the alkyl group or alkoxy group includes a methyl group. , A methoxy group, an ethoxy group, and the like.
- R 15 and R 16 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 17 and R 18 are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group or the like, and the alkyl group is a methyl group or 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 (5) 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 in the molecule may exist as a hydrolysis product in the sol.
- the polysiloxane compound having an alkoxy group in the molecule and Decomposition products may be mixed. Further, in the polysiloxane compound having an alkoxy group in the molecule, all of the alkoxy groups in the molecule may be hydrolyzed or partially hydrolyzed.
- polysiloxane compounds may be used alone or in admixture of two or more.
- the content of the silicon compounds contained in the sol can be 5 to 50 parts by mass with respect to 100 parts by mass of the total sol, but may be 10 to 30 parts by mass. By making it 5 parts by mass or more, it becomes easy to obtain good reactivity, and by making it 50 parts by mass or less, it becomes easy to obtain good compatibility.
- the total content of silicon compounds and polysiloxane compounds can be 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of sol. May be 10 to 30 parts by mass.
- the ratio of the content of the silicon compounds and the content of the hydrolysis product of the polysiloxane compounds can be 0.5: 1 to 4: 1, but is 1: 1 to 2: 1. It may be.
- 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 to 20 parts by mass with respect to 100 parts by mass of the total sol, but may be 4 to 15 parts by mass.
- the content By setting the content to 1 part by mass or more, it becomes easy to impart an appropriate strength to the airgel, and it becomes easy to obtain an airgel composite having excellent shrinkage resistance during drying.
- the airgel composite of this embodiment can have a structure represented by the following general formula (6).
- R 19 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 this embodiment can have a structure represented by the following general formula (7).
- R 20 and R 21 each independently 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 this embodiment can have a structure represented by the following general formula (8).
- R 22 represents an alkylene group.
- examples of the alkylene group include an alkylene group having 1 to 10 carbon atoms, and examples of the alkylene group include an ethylene group and a hexylene group.
- 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 is obtained in a sol generation step, a wet gel generation step in which the sol obtained in the sol generation step is gelled and then aged to obtain a wet gel, and the wet gel generation step.
- the wet gel is washed and (if necessary) solvent-replaced, and the washing and solvent-substituted wet gel is dried by a production method mainly comprising a drying process.
- the sol is a state before the gelation reaction occurs, and in the present embodiment, the silicon compounds, in some cases polysiloxane compounds, and silica particles are dissolved or dispersed in a solvent.
- the wet gel means a gel solid in a wet state that contains a liquid medium but does not have fluidity.
- the sol production step is a step of producing a sol by mixing the above-described silicon compound, optionally a polysiloxane compound, silica particles, and a solvent and hydrolyzing them.
- Silica particles may be mixed in the state of a dispersion dispersed in a solvent.
- an acid catalyst may be further added to the solvent in order to promote the hydrolysis reaction.
- a surfactant, a thermally hydrolyzable compound, and 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 moles with respect to 1 mole of the total amount of the silicon compound and polysiloxane compound, but may be 4 to 6.5. 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.
- Acid catalysts include hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, odorous 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 and the polysiloxane compound.
- 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 examples include those containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group, and those containing a hydrophilic part such as polyoxypropylene.
- examples of those 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.
- hydrophilic parts such as polyoxypropylene, the polyoxypropylene alkyl ether, the block copolymer of polyoxyethylene and polyoxypropylene, etc. are mentioned.
- 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 amount of the surfactant added depends on the type of the surfactant or the types and amounts of the silicon compound and the polysiloxane compound.
- the amount of the surfactant added is 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the silicon compound and the polysiloxane compound.
- the amount can be 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 of the total amount of the silicon compound and the polysiloxane compound.
- the added amount may be 2 to 150 parts by mass.
- the hydrolysis in the sol production step depends on the type and amount 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. For 10 minutes to 24 hours, or in a temperature environment of 50 to 60 ° C. for 5 minutes to 8 hours.
- the hydrolyzable functional group in a silicon compound and a polysiloxane compound is fully hydrolyzed, and the hydrolysis product of a silicon compound and the hydrolysis product of a polysiloxane compound can be obtained more reliably.
- 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 remain in the airgel composite after drying, and thus does not impair water resistance, and is economical. You may use said base catalyst individually or in mixture of 2 or more types.
- the dehydration condensation reaction, dealcoholization condensation reaction, or both of the silicon compounds, polysiloxane compounds, and silica particles in the sol can be promoted, and the gelation of the sol It can be performed in a shorter time. 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 silicon compounds and polysiloxane compounds, 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. This is because the silanol groups, reactive groups, or both of the silicon compounds and polysiloxane compounds in the sol form hydrogen bonds, chemical bonds, or a combination of these bonds with the silanol groups of the silica particles. I guess that is to do.
- 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.
- cleaning can be repeatedly performed using water or an organic solvent, for example. 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 those 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), 2-ch
- 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 that the drying is accelerated 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 obtained by molding 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 formed by molding at least one fiber-shaped raw material selected from the group consisting of organic, inorganic, and metal. Paper, non-woven fabric (including glass mat), organic fiber cloth, glass cloth, etc. Can be mentioned.
- the foil-like support member is a metal raw material formed into a thin film, and examples thereof include aluminum foil and copper foil.
- the porous support member has a porous structure using at least one selected from the group consisting of organic, inorganic and metal as a raw material, for example, a porous organic material such as polyurethane foam, a porous material such as a zeolite sheet, etc. Examples thereof include porous materials such as inorganic materials, porous metal sheets, and porous aluminum sheets.
- the support member with the airgel composite can be manufactured, for example, as follows. First, a sol is prepared according to the sol generation process described above. After applying this onto the support member using a film applicator or the like, or impregnating the support member with the film applicator, a film-like support member with a wet gel is obtained according to the wet gel generation step described above. Then, the obtained film-like support member with wet gel is subjected to cleaning and solvent replacement according to the above-described cleaning and solvent replacement steps, and further dried according to the above-described drying step, whereby the support member with an airgel composite is provided. Can be obtained.
- the thickness of the airgel composite formed on the film-like support member or 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] 80.0 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: “DMDMS” (hereinafter abbreviated as “20.0 mass parts”) and PL-20 as a silica particle-containing raw material (details of PL-20 are shown 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 at 40 ° C. for 96 hours under normal pressure, and then further dried at 150 ° C. for 2 hours, whereby the structures represented by the above general formulas (6) and (7) are obtained.
- 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] 60.0 parts by mass of MTMS as a silicon compound and 40.0 parts by mass of DMDMS, 100.0 parts by mass of PL-2L as a silica particle-containing raw material, 40.0 parts by mass of water and 80.0 parts by mass of methanol 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 2. 40.0 parts by mass of 5% aqueous ammonia as a base catalyst was added to the obtained sol 2, gelled at 60 ° C., and then aged at 80 ° C. for 24 hours to obtain wet gel 2. Then, the airgel composite 2 which has the structure represented by the said General formula (6) and (7) was obtained like Example 1 using the obtained wet gel 2.
- Example 3 [Wet gel, airgel composite] 60.0 parts by mass of MTMS as a silicon compound, 40.0 parts by mass of bistrimethoxysilylhexane “KBM-3066” (manufactured by Shin-Etsu Chemical Co., Ltd., product name), and ST-OZL-35 as a silica particle-containing raw material 57.0 parts by mass, 83.0 parts by mass of water and 80.0 parts by mass of methanol, 0.10 parts by mass of acetic acid as an acid catalyst, and cetyltrimethylammonium bromide (as a cationic surfactant) 20.0 parts by mass of Wako Pure Chemical Industries, Ltd.
- KBM-3066 bistrimethoxysilylhexane
- ST-OZL-35 as a silica particle-containing raw material 57.0 parts by mass
- 83.0 parts by mass of water and 80.0 parts by mass of methanol 0.10 parts by mass of acetic acid as an acid catalyst
- 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 was mixed as a decomposable compound, and 70.0 parts by mass of MTMS and 30.0 parts by mass of DMDMS were added thereto as a silicon compound, and reacted at 25 ° C. for 2 hours to obtain sol 4. The obtained sol 4 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 4. Then, the airgel composite 4 which has the structure represented by the said General formula (6) and (7) was obtained like Example 1 using the obtained wet gel 4.
- Example 5 [Wet gel, airgel composite] 200.0 parts by mass of ST-OXS 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.
- the mixture was mixed with 0 part by mass, 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 5.
- 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 (6) and (7) was obtained like Example 1 using the obtained wet gel 5.
- Example 6 [Wet gel, airgel composite] 100.0 parts by mass of PL-2L-D 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, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea is mixed as a thermohydrolyzable compound, 60.0 parts by mass of MTMS and 40.0 parts by mass of DMDMS are added as silicon compounds to this, and reacted at 25 ° C. for 2 hours to obtain sol 6. It was. The obtained sol 6 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 6. Then, the airgel composite 6 which has the structure represented by the said General formula (6) and (7) was obtained like Example 1 using the obtained wet gel 6.
- Example 7 [Wet gel, airgel composite] As a raw material containing silica particles, 87.0 parts by mass of PL-7, 113.0 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 was mixed as a decomposable compound, and 60.0 parts by mass of MTMS and 40.0 parts by mass of DMDMS were added thereto as a silicon compound, and reacted at 25 ° C. for 2 hours to obtain sol 7. The obtained sol 7 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 7. Thereafter, an airgel composite 7 having a structure represented by the general formulas (6) and (7) was obtained using the obtained wet gel 7 in the same manner as in Example 1.
- Example 8 [Wet gel, airgel composite] 167.0 parts by mass of PL-1 as a silica particle-containing raw material, 33.0 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 was mixed as a decomposable compound, and 60.0 parts by mass of MTMS and 40.0 parts by mass of DMDMS were added thereto as a silicon compound, and reacted at 25 ° C. for 2 hours to obtain sol 8.
- the obtained sol 8 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 8.
- the airgel composite 8 which has the structure represented by the said General formula (6) and (7) was obtained like Example 1 using the obtained wet gel 8.
- Example 9 [Wet gel, airgel composite] 10.0 parts by mass of AEROSIL 90 as a raw material containing silica particles, 190.0 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 hydrolyzability 120.0 parts by mass of urea was mixed as a compound, and 60.0 parts by mass of MTMS and 40.0 parts by mass of DMDMS were added thereto as a silicon compound, and reacted at 25 ° C. for 2 hours to obtain sol 9. The obtained sol 9 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 9. Thereafter, using the obtained wet gel 9, the airgel composite 9 having the structure represented by the general formulas (6) and (7) was obtained in the same manner as in Example 1.
- Example 10 [Wet gel, airgel composite] 10.0 parts by mass of SO-C2 as a raw material containing silica particles, 190.0 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, and 60.0 parts by mass of MTMS and 40.0 parts by mass of bistrimethoxysilylhexane are added to this as a silicon compound, followed by reaction at 25 ° C. for 2 hours to obtain sol 10 Obtained.
- the obtained sol 10 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 10. Then, the airgel composite 10 which has the structure represented by the said General formula (6) and (8) was obtained like Example 1 using the obtained wet gel 10.
- Example 11 [Wet gel, airgel composite] 100.0 parts by mass of ST-OYL 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, and polyoxyethylene and polyoxypropylene as nonionic surfactants 20.0 parts by mass of the block copolymer F-127 (manufactured by BASF, product name) and 120.0 parts by mass of urea as a thermally hydrolyzable compound were mixed with 80.
- MTMS as a silicon compound.
- Example 12 [Wet gel, airgel composite] 200.0 parts by mass of PL-06L 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.
- MTMS as a silicon compound
- CTAB as a cationic surfactant
- 120. urea as a thermohydrolyzable compound.
- MTMS as a silicon compound
- the “polysiloxane compound A” was synthesized as follows. First, 100.0 masses of dimethylpolysiloxane XC96-723 (product name, manufactured by Momentive) having silanol groups at both ends in a 1-liter three-necked flask equipped with a stirrer, a thermometer, and a Dimroth condenser. Parts, 181.3 parts by mass of methyltrimethoxysilane 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 13 [Wet gel, airgel composite] 100.0 parts by mass of PL-20 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 as a decomposable compound, 60.0 parts by mass of MTMS as a silicon compound, and trifunctional alkoxy modification at both ends having a structure represented by the above general formula (5) as a polysiloxane compound 40.0 parts by mass of a polysiloxane compound (hereinafter referred to as “polysiloxane compound B”) was added and reacted at 25 ° C.
- polysiloxane compound B a polysiloxane compound
- 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.
- Example 14 [Wet gel, airgel composite] 100.0 parts by mass of PL-20 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 was mixed as a decomposable compound, 60.0 parts by mass of MTMS and 20.0 parts by mass of DMDMS as silicon compounds, and 20.0 parts by mass of X-22-160AS as a polysiloxane compound.
- a sol 14 was obtained by reacting at 25 ° C. for 2 hours. The obtained sol 14 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 14. Thereafter, an airgel composite 14 having a structure represented by the general formulas (1), (6) and (7) was obtained in the same manner as in Example 1 by using the obtained wet gel 14.
- Example 15 [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 was mixed as a decomposable compound, 60.0 parts by mass of MTMS and 20.0 parts by mass of DMDMS as silicon compounds, and 20.0 parts by mass of polysiloxane compound A as a polysiloxane compound.
- sol 15 was obtained by reaction at 25 ° C. for 2 hours. The obtained sol 15 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 15. Then, the airgel composite 15 which has the structure represented by the said General formula (3), (6) and (7) was obtained like Example 1 using the obtained wet gel 15.
- Example 16 [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 16. The obtained sol 16 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 16. Thereafter, an airgel composite 16 having a structure represented by the general formulas (2), (6), and (7) was obtained using the obtained wet gel 16 in the same manner as in Example 1.
- Example 17 [Wet gel, airgel composite] 50.0 parts by mass of PL-2L and 50.0 parts by mass of PL-20 as raw materials containing silica particles, 100.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, and as a cationic surfactant 20.0 parts by mass of CTAB and 120.0 parts by mass of urea as a thermally hydrolyzable compound were mixed, and 60.0 parts by mass of MTMS and 40.0 parts by mass of DMDMS were added thereto as a silicon compound.
- a sol 17 was obtained by reacting for a period of time. The obtained sol 17 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 17. Thereafter, an airgel composite 17 having a structure represented by the general formulas (6) and (7) was obtained in the same manner as in Example 1 by using the obtained wet gel 17.
- Example 18 [Wet gel, airgel composite] 100.0 parts by mass of PL-2L as a raw material containing silica particles, 50.0 parts by mass of ST-OZL-35, 50.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, cationic surface activity 20.0 parts by mass of CTAB as an agent, 120.0 parts by mass of urea as a thermally hydrolyzable compound, 60.0 parts by mass of MTMS and 20.0 parts by mass of DMDMS as a silicon compound, and a polysiloxane compound As a result, 20.0 parts by mass of polysiloxane compound A was added and reacted at 25 ° C. for 2 hours to obtain sol 18.
- the obtained sol 18 was gelled at 60 ° C. and then aged at 80 ° C. for 24 hours to obtain a wet gel 18. Thereafter, an airgel composite 18 having a structure represented by the general formulas (3), (6) and (7) was obtained in the same manner as in Example 1 by using the obtained wet gel 18.
- Example 19 [Wet gel, airgel composite]
- the wet gel 17 obtained above 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. Next, the washed wet gel was immersed in 2500.0 parts by mass of 2-propanol, and solvent substitution was performed at 60 ° C. for 12 hours. This solvent replacement operation was performed three times while exchanging with new 2-propanol.
- Example 20 [Wet gel, airgel composite] Using the wet gel 18 obtained above, an airgel composite 20 having a structure represented by the general formulas (3), (6) and (7) was obtained in the same manner as in Example 19.
- Example 21 [Wet gel, airgel composite]
- the wet gel 15 obtained above 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. Next, the washed wet gel is dried at 60 ° C. for 2 hours and at 100 ° C. for 3 hours under solvent pressure without solvent substitution, and then further dried at 150 ° C. for 2 hours.
- the airgel composite 21 having the structure represented by (3), (6) and (7) was obtained.
- Each support member with a wet gel obtained using the wet gel 15 was immersed in 100 mL of methanol and washed at 60 ° C. for 2 hours. Next, each washed support member with wet gel was dried at 60 ° C. for 30 minutes and at 100 ° C. for 1 hour under normal pressure.
- a film-like support member 21 with an airgel composite, a sheet-like support member 21 with an airgel composite, a foil-like support member 21 with an airgel composite, and a porous support member 21 with an airgel composite were obtained.
- Example 22 [Wet gel, airgel composite] Using the wet gel 16 obtained above, an airgel composite 22 having a structure represented by the general formulas (2), (6) and (7) was obtained in the same manner as in Example 21.
- 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 the Si raw materials (silicon compounds and polysiloxane compounds), and the addition amount of the 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 15, (a) 10,000 times, (b) 50,000 times, (c) 200,000 times, and (d ) SEM images observed at 350,000 times.
- 4 shows the surface of the airgel composite in the foil-like support member with the airgel composite obtained in Example 16, 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 15 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 16 also has a three-dimensional network skeleton.
- the cluster structure is unique. In this example, it does not have a structure in which particles and particles are connected in a bead shape as in a normal airgel, and the connection part of particles and particles seems to be densely filled with an airgel component (silicone). It is observed. Moreover, since the particle diameter of the particle
- 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 16 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
- FIG. 5 is SEM images obtained by observing the surface of the airgel composite in the foil-like support member with an airgel composite obtained in Example 23 at (a) 50,000 times and (b) 200,000 times, respectively.
- FIG. 6 is SEM images obtained by observing the surface of the airgel composite in the foil-like support member with the airgel composite obtained in Example 24 at (a) 50,000 times and (b) 200,000 times, respectively.
- Example 23 A foil with an airgel composite as in Example 15, except that PL-3L (a product name, sol in which spherical colloidal silica having an average primary particle diameter of 35 nm is dispersed) was used as a silica particle-containing raw material. A shaped support member was obtained.
- Example 24 A foil with an airgel composite as in Example 15 except that HL-3L (a product name, a sol in which spherical colloidal silica having an average primary particle size of 30 nm is dispersed) was used as a silica particle-containing raw material. A shaped support member was obtained.
- the airgel composites obtained using PL-3L and HL-3L also have a three-dimensional network skeleton.
- particles derived from silica particles having a particle size of about 40 nm and airgel particles having a particle size of about 20 to 30 nm were mainly observed.
- particles derived from silica particles having a particle size of about 40 nm and airgel particles having a particle size of about 10 nm were mainly observed. Comparing the two, the airgel composite obtained using PL-3L (FIG. 5) is more derived from silica particles than the airgel composite obtained using HL-3L (FIG. 6). The particles were closely connected via the airgel component.
- PL-3L can improve the strength of the airgel composite as compared with HL-3L. Since PL-3L has more silanol groups per gram than HL-3L, it is presumed that the airgel component was generated at a higher rate and the airgel component in the obtained airgel composite was easily grown in the form of particles.
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Abstract
Description
狭義には、湿潤ゲルに対して超臨界乾燥法を用いて得られた乾燥ゲルをエアロゲル、大気圧下での乾燥により得られた乾燥ゲルをキセロゲル、凍結乾燥により得られた乾燥ゲルをクライオゲルと称するが、本実施形態においては、湿潤ゲルのこれらの乾燥手法によらず、得られた低密度の乾燥ゲルをエアロゲルと称する。すなわち、本実施形態においてエアロゲルとは、広義のエアロゲルである「Gel comprised of a microporous solid in which the dispersed phase is a gas(分散相が気体である微多孔性固体から構成されるゲル)」を意味するものである。一般的にエアロゲルの内部は網目状の微細構造となっており、2~20nm程度のエアロゲル粒子が結合したクラスター構造を有している。このクラスターにより形成される骨格間には、100nmに満たない細孔があり、三次元的に微細な多孔性の構造をしている。なお、本実施形態におけるエアロゲルは、シリカを主成分とするシリカエアロゲルである。シリカエアロゲルとしては、メチル基等の有機基又は有機鎖を導入した、いわゆる有機-無機ハイブリッド化されたシリカエアロゲルが挙げられる。なお、本実施形態のエアロゲル複合体は、エアロゲル中にシリカ粒子が複合化されながらも、上記エアロゲルの特徴であるクラスター構造を有しており、三次元的に微細な多孔性の構造を有している。
本実施形態のエアロゲル複合体において、大気圧下、25℃における熱伝導率は0.03W/m・K以下とすることができるが、0.025W/m・K以下であってもよく、0.02W/m・K以下であってもよい。熱伝導率が0.03W/m・K以下であることにより、高性能断熱材であるポリウレタンフォーム以上の断熱性を得ることができる。なお、熱伝導率の下限値は特に限定されないが、例えば、0.01W/m・Kとすることができる。
刃角約20~25度の刃を用いて、エアロゲル複合体を150mm×150mm×100mmのサイズに加工し、測定サンプルとする。なお、HFM436Lambdaにおける推奨サンプルサイズは300mm×300mm×100mmであるが、上記サンプルサイズで測定した際の熱伝導率は、推奨サンプルサイズで測定した際の熱伝導率と同程度の値となることを確認済みである。次に、面の平行を確保するために、必要に応じて#1500以上の紙やすりで測定サンプルを整形する。そして、熱伝導率測定前に、定温乾燥機「DVS402」(ヤマト科学株式会社製、製品名)を用いて、大気圧下、100℃で30分間、測定サンプルを乾燥する。次いで、測定サンプルをデシケータ中に移し、25℃まで冷却する。これにより、熱伝導率測定用の測定サンプルを得る。
測定条件は、大気圧下、平均温度25℃とする。上記のとおり得られた測定サンプルを0.3MPaの荷重にて上部及び下部ヒーター間に挟み、温度差ΔTを20℃とし、ガードヒーターによって一次元の熱流になるように調整しながら、測定サンプルの上面温度、下面温度等を測定する。そして、測定サンプルの熱抵抗RSを次式より求める。
RS=N((TU-TL)/Q)-RO
式中、TUは測定サンプル上面温度を示し、TLは測定サンプル下面温度を示し、ROは上下界面の接触熱抵抗を示し、Qは熱流束計出力を示す。なお、Nは比例係数であり、較正試料を用いて予め求めておく。
λ=d/RS
式中、dは測定サンプルの厚さを示す。
本実施形態のエアロゲル複合体において、25℃における圧縮弾性率は3MPa以下とすることができるが、2MPa以下であってもよく、1MPa以下であってもよく、0.5MPa以下であってもよい。圧縮弾性率が3MPa以下であることにより、取り扱い性が優れるエアロゲル複合体とし易くなる。なお、圧縮弾性率の下限値は特に限定されないが、例えば、0.05MPaとすることができる。
本実施形態のエアロゲル複合体において、25℃における変形回復率は90%以上とすることができるが、94%以上であってもよく、98%以上であってもよい。変形回復率が90%以上であることにより、優れた強度、変形に対する優れた柔軟性等をより得易くなる。なお、変形回復率の上限値は特に限定されないが、例えば、100%又は99%とすることができる。
本実施形態のエアロゲル複合体において、25℃における最大圧縮変形率は80%以上とすることができるが、83%以上であってもよく、86%以上であってもよい。最大圧縮変形率が80%以上であることにより、優れた強度、変形に対する優れた柔軟性等をより得易くなる。なお、最大圧縮変形率の上限値は特に限定されないが、例えば、90%とすることができる。
刃角約20~25度の刃を用いて、エアロゲル複合体を7.0mm角の立方体(サイコロ状)に加工し、測定サンプルとする。次に、面の平行を確保するために、必要に応じて#1500以上の紙やすりで測定サンプルを整形する。そして、測定前に、定温乾燥機「DVS402」(ヤマト科学株式会社製、製品名)を用いて、大気圧下、100℃で30分間、測定サンプルを乾燥する。次いで測定サンプルをデシケータ中に移し、25℃まで冷却する。これにより、圧縮弾性率、変形回復率及び最大圧縮変形率測定用の測定サンプルを得る。
500Nのロードセルを使用する。また、ステンレス製の上圧盤(φ20mm)、下圧盤(φ118mm)を圧縮測定用冶具として用いる。測定サンプルをこれら冶具の間にセットし、1mm/minの速度で圧縮を行い、25℃における測定サンプルサイズの変位等を測定する。測定は、500N超の負荷をかけた時点又は測定サンプルが破壊した時点で終了とする。ここで、圧縮ひずみεは次式より求めることができる。
ε=Δd/d1
式中、Δdは負荷による測定サンプルの厚みの変位(mm)を示し、d1は負荷をかける前の測定サンプルの厚み(mm)を示す。
また、圧縮応力σ(MPa)は、次式より求めることができる。
σ=F/A
式中、Fは圧縮力(N)を示し、Aは負荷をかける前の測定サンプルの断面積(mm2)を示す。
E=(σ2-σ1)/(ε2-ε1)
式中、σ1は圧縮力が0.1Nにおいて測定される圧縮応力(MPa)を示し、σ2は圧縮力が0.2Nにおいて測定される圧縮応力(MPa)を示し、ε1は圧縮応力σ1において測定される圧縮ひずみを示し、ε2は圧縮応力σ2において測定される圧縮ひずみを示す。
変形回復率=(d3-d2)/(d1-d2)×100
最大圧縮変形率=(d1-d2)/d1×100
本実施形態のエアロゲル複合体において、細孔3のサイズ、すなわち平均細孔径は5~1000nmとすることができるが、25~500nmであってもよい。平均細孔径が5nm以上であることにより、柔軟性に優れるエアロゲル複合体が得易くなり、また、1000nm以下であることにより、断熱性に優れるエアロゲル複合体が得易くなる。
本実施形態のエアロゲル複合体におけるエアロゲル成分としては、以下の態様が挙げられる。これらの態様を採用することにより、エアロゲル複合体の断熱性及び柔軟性を所望の水準に制御することが容易となる。ただし、これらの態様の各々を採用することは、必ずしも本実施形態にて規定するエアロゲル複合体を得ることが目的ではない。各々の態様を採用することで、各々の態様に応じた熱伝導率及び圧縮弾性率を有するエアロゲル複合体を得ることができる。したがって、用途に応じた断熱性及び柔軟性を有するエアロゲル複合体を提供することができる。
本実施形態のエアロゲル複合体は、支柱部及び橋かけ部を備えるラダー型構造を有するエアロゲル複合体であり、かつ、橋かけ部が下記一般式(2)で表される構造を有するエアロゲル複合体であってもよい。このようなラダー型構造をエアロゲル成分としてエアロゲル複合体の骨格中に導入することにより、耐熱性及び機械的強度を向上させることができる。なお、本実施形態において「ラダー型構造」とは、2本の支柱部(struts)と支柱部同士を連結する橋かけ部(bridges)とを有するもの(いわゆる「梯子」の形態を有するもの)である。本態様において、エアロゲル複合体の骨格がラダー型構造からなっていてもよいが、エアロゲル複合体が部分的にラダー型構造を有していてもよい。
本実施形態のエアロゲル複合体は、シリカ粒子と、分子内に加水分解性の官能基を有するシリコン化合物及び該シリコン化合物の加水分解生成物からなる群より選択される少なくとも一種(以下、これらのシリコン化合物等を総称して「シリコン化合物類」という場合がある)と、を含有するゾルから生成された湿潤ゲルを乾燥して得られるものであってもよい。なお、これまで述べてきたエアロゲル複合体も、このように、シリカ粒子と、シリコン化合物類とを含有するゾルから生成された湿潤ゲルを乾燥することで得られるものであってもよい。
次に、エアロゲル複合体の製造方法について説明する。エアロゲル複合体の製造方法は、特に限定されないが、例えば、以下の方法により製造することができる。
ゾル生成工程は、上述のシリコン化合物と、場合によりポリシロキサン化合物と、シリカ粒子と、溶媒とを混合し、加水分解させてゾルを生成する工程である。なお、シリカ粒子は、溶媒に分散された分散液の状態で混合してもよい。本工程においては、加水分解反応を促進させるため、溶媒中にさらに酸触媒を添加してもよい。また、特許第5250900号に示されるように、溶媒中に界面活性剤、熱加水分解性化合物等を添加することもできる。さらに、熱線輻射抑制等を目的として、溶媒中にカーボングラファイト、アルミニウム化合物、マグネシウム化合物、銀化合物、チタン化合物等の成分を添加してもよい。
湿潤ゲル生成工程は、ゾル生成工程で得られたゾルをゲル化し、その後熟成して湿潤ゲルを得る工程である。本工程では、ゲル化を促進させるため塩基触媒を用いることができる。
洗浄及び溶媒置換工程は、上記湿潤ゲル生成工程により得られた湿潤ゲルを洗浄する工程(洗浄工程)と、湿潤ゲル中の洗浄液を乾燥条件(後述の乾燥工程)に適した溶媒に置換する工程(溶媒置換工程)を有する工程である。洗浄及び溶媒置換工程は、湿潤ゲルを洗浄する工程を行わず、溶媒置換工程のみを行う形態でも実施可能であるが、湿潤ゲル中の未反応物、副生成物等の不純物を低減し、より純度の高いエアロゲル複合体の製造を可能にする観点からは、湿潤ゲルを洗浄してもよい。なお、本実施形態においては、ゲル中にシリカ粒子が含まれていることから、後述するように溶媒置換工程は必ずしも必須ではない。
乾燥工程では、上記のとおり洗浄及び(必要に応じ)溶媒置換した湿潤ゲルを乾燥させる。これにより、最終的にエアロゲル複合体を得ることができる。
本実施形態のエアロゲル複合体つき支持部材は、これまで説明したエアロゲル複合体と、当該エアロゲル複合体を担持する支持部材と、を備えるものである。このようなエアロゲル複合体つき支持部材であれば、高断熱性と優れた屈曲性とを発現することができる。
本実施形態の断熱材は、これまで説明したエアロゲル複合体を備えるものであり、高断熱性と優れた屈曲性とを有している。なお、上記エアロゲル複合体の製造方法により得られるエアロゲル複合体をそのまま(必要に応じ所定の形状に加工し)断熱材とすることができる。
[湿潤ゲル、エアロゲル複合体]
シリコン化合物としてメチルトリメトキシシランLS-530(信越化学工業株式会社製、製品名:以下『MTMS』と略記)を80.0質量部及びジメチルジメトキシシランLS-520(信越化学工業株式会社製、製品名:以下『DMDMS』と略記)を20.0質量部、並びにシリカ粒子含有原料としてPL-20(PL-20の詳細については表1に記載。シリカ粒子含有原料について以下同様。)を100.0質量部、水を40.0質量部及びメタノールを80.0質量部混合し、これに酸触媒として酢酸を0.10質量部加え、25℃で2時間反応させてゾル1を得た。得られたゾル1に、塩基触媒として5%濃度のアンモニア水を40.0質量部加え、60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル1を得た。
・エアロゲル複合体付きフィルム状支持部材
上記ゾル1を、(縦)300mm×(横)270mm×(厚)12μmのポリエチレンテレフタレート製フィルムに、ゲル化後の厚みが40μmとなるようにフィルムアプリケーター(テスター産業株式会社製、PI-1210)を用いて塗布し、60℃で3時間ゲル化した後、80℃で24時間熟成して湿潤ゲル付きフィルム状支持部材1を得た。
上記ゾル1を、(縦)300mm×(横)270mm×(厚)100μmのEガラスクロスに、ゲル化後のシート状支持部材の厚みが120μmとなるように含浸し、60℃で3時間ゲル化した後、80℃で24時間熟成して湿潤ゲル付きシート状支持部材1を得た。
上記ゾル1を、(縦)300mm×(横)270mm×(厚)12μmのアルミニウム箔に、ゲル化後の厚みが40μmとなるようにフィルムアプリケーターを用いて塗布し、60℃で3時間ゲル化した後、80℃で24時間熟成して湿潤ゲル付き箔状支持部材1を得た。
上記ゾル1を、(縦)300mm×(横)270mm×(厚)10mmの軟質ウレタンフォームに、ゲル化後の多孔質支持部材の厚みが10mmとなるように含浸し、60℃で3時間ゲル化した後、80℃で24時間熟成して湿潤ゲル付き多孔質支持部材1を得た。
[湿潤ゲル、エアロゲル複合体]
シリコン化合物としてMTMSを60.0質量部及びDMDMSを40.0質量部、並びにシリカ粒子含有原料としてPL-2Lを100.0質量部、水を40.0質量部及びメタノールを80.0質量部混合し、これに酸触媒として酢酸を0.10質量部加え、25℃で2時間反応させてゾル2を得た。得られたゾル2に、塩基触媒として5%濃度のアンモニア水を40.0質量部加え、60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル2を得た。その後、得られた湿潤ゲル2を用いて、実施例1と同様にして上記一般式(6)及び(7)で表される構造を有するエアロゲル複合体2を得た。
上記ゾル2を用いて、実施例1と同様にして、エアロゲル複合体付き支持部材2、エアロゲル複合体付きシート状支持部材2、エアロゲル複合体付き箔状支持部材2及びエアロゲル複合体付き多孔質支持部材2を得た。
[湿潤ゲル、エアロゲル複合体]
シリコン化合物としてMTMSを60.0質量部及びビストリメトキシシリルへキサン「KBM-3066」(信越化学工業株式会社製、製品名)を40.0質量部、並びにシリカ粒子含有原料としてST-OZL-35を57.0質量部、水を83.0質量部及びメタノールを80.0質量部混合し、これに酸触媒として酢酸を0.10質量部、カチオン系界面活性剤として臭化セチルトリメチルアンモニウム(和光純薬工業株式会社製:以下『CTAB』と略記)を20.0質量部加え、25℃で2時間反応させてゾル3を得た。得られたゾル3に、塩基触媒として5%濃度のアンモニア水を40.0質量部加え、60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル3を得た。その後、得られた湿潤ゲル3を用いて、実施例1と同様にして上記一般式(6)及び(8)で表される構造を有するエアロゲル複合体3を得た。
上記ゾル3を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材3、エアロゲル複合体付きシート状支持部材3、エアロゲル複合体付き箔状支持部材3及びエアロゲル複合体付き多孔質支持部材3を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてPL-2Lを100.0質量部、水を100.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを70.0質量部及びDMDMSを30.0質量部加え、25℃で2時間反応させてゾル4を得た。得られたゾル4を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル4を得た。その後、得られた湿潤ゲル4を用いて、実施例1と同様にして上記一般式(6)及び(7)で表される構造を有するエアロゲル複合体4を得た。
上記ゾル4を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材4、エアロゲル複合体付きシート状支持部材4、エアロゲル複合体付き箔状支持部材4及びエアロゲル複合体付き多孔質支持部材4を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてST-OXSを200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを40.0質量部加え、25℃で2時間反応させてゾル5を得た。得られたゾル5を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル5を得た。その後、得られた湿潤ゲル5を用いて、実施例1と同様にして上記一般式(6)及び(7)で表される構造を有するエアロゲル複合体5を得た。
上記ゾル5を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材5、エアロゲル複合体付きシート状支持部材5、エアロゲル複合体付き箔状支持部材5及びエアロゲル複合体付き多孔質支持部材5を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてPL-2L―Dを100.0質量部、水を100.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを40.0質量部加え、25℃で2時間反応させてゾル6を得た。得られたゾル6を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル6を得た。その後、得られた湿潤ゲル6を用いて、実施例1と同様にして上記一般式(6)及び(7)で表される構造を有するエアロゲル複合体6を得た。
上記ゾル6を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材6、エアロゲル複合体付きシート状支持部材6、エアロゲル複合体付き箔状支持部材6及びエアロゲル複合体付き多孔質支持部材6を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてPL-7を87.0質量部、水を113.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを40.0質量部加え、25℃で2時間反応させてゾル7を得た。得られたゾル7を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル7を得た。その後、得られた湿潤ゲル7を用いて、実施例1と同様にして上記一般式(6)及び(7)で表される構造を有するエアロゲル複合体7を得た。
上記ゾル7を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材7、エアロゲル複合体付きシート状支持部材7、エアロゲル複合体付き箔状支持部材7及びエアロゲル複合体付き多孔質支持部材7を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてPL-1を167.0質量部、水を33.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを40.0質量部加え、25℃で2時間反応させてゾル8を得た。得られたゾル8を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル8を得た。その後、得られた湿潤ゲル8を用いて、実施例1と同様にして上記一般式(6)及び(7)で表される構造を有するエアロゲル複合体8を得た。
上記ゾル8を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材8、エアロゲル複合体付きシート状支持部材8、エアロゲル複合体付き箔状支持部材8及びエアロゲル複合体付き多孔質支持部材8を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてAEROSIL90を10.0質量部、水を190.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを40.0質量部加え、25℃で2時間反応させてゾル9を得た。得られたゾル9を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル9を得た。その後、得られた湿潤ゲル9を用いて、実施例1と同様にして上記一般式(6)及び(7)で表される構造を有するエアロゲル複合体9を得た。
上記ゾル9を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材9、エアロゲル複合体付きシート状支持部材9、エアロゲル複合体付き箔状支持部材9及びエアロゲル複合体付き多孔質支持部材9を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてSO-C2を10.0質量部、水を190.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びビストリメトキシシリルヘキサンを40.0質量部加え、25℃で2時間反応させてゾル10を得た。得られたゾル10を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル10を得た。その後、得られた湿潤ゲル10を用いて、実施例1と同様にして上記一般式(6)及び(8)で表される構造を有するエアロゲル複合体10を得た。
上記ゾル10を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材10、エアロゲル複合体付きシート状支持部材10、エアロゲル複合体付き箔状支持部材10及びエアロゲル複合体付き多孔質支持部材10を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてST-OYLを100.0質量部、水を100.0質量部、酸触媒として酢酸を0.10質量部、非イオン性界面活性剤として、ポリオキシエチレンとポリオキシプロピレンとのブロック共重合体であるF-127(BASF社製、製品名)を20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを80.0質量部及び上記一般式(4)で表される構造を有するポリシロキサン化合物としてX-22-160ASを20.0質量部加え、25℃で2時間反応させてゾル11を得た。得られたゾル11を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル11を得た。その後、得られた湿潤ゲル11を用いて、実施例1と同様にして上記一般式(1)及び(6)で表される構造を有するエアロゲル複合体11を得た。
上記ゾル11を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材11、エアロゲル複合体付きシート状支持部材11、エアロゲル複合体付き箔状支持部材11及びエアロゲル複合体付き多孔質支持部材11を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてPL-06Lを200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを80.0質量部及びポリシロキサン化合物として上記一般式(5)で表される構造を有する両末端2官能アルコキシ変性ポリシロキサン化合物(以下、「ポリシロキサン化合物A」という)を20.0質量部加え、25℃で2時間反応させてゾル12を得た。得られたゾル12を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル12を得た。その後、得られた湿潤ゲル12を用いて、実施例1と同様にして上記一般式(3)及び(6)で表される構造を有するエアロゲル複合体12を得た。
上記ゾル12を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材12、エアロゲル複合体付きシート状支持部材12、エアロゲル複合体付き箔状支持部材12及びエアロゲル複合体付き多孔質支持部材12を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてPL-20を100.0質量部、水を100.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びポリシロキサン化合物として上記一般式(5)で表される構造を有する両末端3官能アルコキシ変性ポリシロキサン化合物(以下、「ポリシロキサン化合物B」という)を40.0質量部加え、25℃で2時間反応させてゾル13を得た。得られたゾル13を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル13を得た。その後、得られた湿潤ゲル13を用いて、実施例1と同様にして上記一般式(2)及び(6)で表される構造を有するエアロゲル複合体13を得た。
上記ゾル13を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材13、エアロゲル複合体付きシート状支持部材13、エアロゲル複合体付き箔状支持部材13及びエアロゲル複合体付き多孔質支持部材13を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてPL-20を100.0質量部、水を100.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを20.0質量部、並びにポリシロキサン化合物としてX-22-160ASを20.0質量部加え、25℃で2時間反応させてゾル14を得た。得られたゾル14を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル14を得た。その後、得られた湿潤ゲル14を用いて、実施例1と同様にして上記一般式(1)、(6)及び(7)で表される構造を有するエアロゲル複合体14を得た。
上記ゾル14を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材14、エアロゲル複合体付きシート状支持部材14、エアロゲル複合体付き箔状支持部材14及びエアロゲル複合体付き多孔質支持部材14を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてPL-2Lを100.0質量部、水を100.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを20.0質量部、並びにポリシロキサン化合物としてポリシロキサン化合物Aを20.0質量部加え、25℃で2時間反応させてゾル15を得た。得られたゾル15を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル15を得た。その後、得られた湿潤ゲル15を用いて、実施例1と同様にして上記一般式(3)、(6)及び(7)で表される構造を有するエアロゲル複合体15を得た。
上記ゾル15を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材15、エアロゲル複合体付きシート状支持部材15、エアロゲル複合体付き箔状支持部材15及びエアロゲル複合体付き多孔質支持部材15を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてST-OZL-35を143.0質量部、水を57.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを20.0質量部、並びにポリシロキサン化合物としてポリシロキサン化合物Bを20.0質量部加え、25℃で2時間反応させてゾル16を得た。得られたゾル16を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル16を得た。その後、得られた湿潤ゲル16を用いて、実施例1と同様にして上記一般式(2)、(6)及び(7)で表される構造を有するエアロゲル複合体16を得た。
上記ゾル16を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材16、エアロゲル複合体付きシート状支持部材16、エアロゲル複合体付き箔状支持部材16及びエアロゲル複合体付き多孔質支持部材16を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてPL-2Lを50.0質量部及びPL-20を50.0質量部、水を100.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部並びに熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを40.0質量部加え、25℃で2時間反応させてゾル17を得た。得られたゾル17を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル17を得た。その後、得られた湿潤ゲル17を用いて、実施例1と同様にして上記一般式(6)及び(7)で表される構造を有するエアロゲル複合体17を得た。
上記ゾル17を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材17、エアロゲル複合体付きシート状支持部材17、エアロゲル複合体付き箔状支持部材17及びエアロゲル複合体付き多孔質支持部材17を得た。
[湿潤ゲル、エアロゲル複合体]
シリカ粒子含有原料としてPL-2Lを100.0質量部及びST-OZL-35を50.0質量部、水を50.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部並びに熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを20.0質量部並びにポリシロキサン化合物としてポリシロキサン化合物Aを20.0質量部加え、25℃で2時間反応させてゾル18を得た。得られたゾル18を60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル18を得た。その後、得られた湿潤ゲル18を用いて、実施例1と同様にして上記一般式(3)、(6)及び(7)で表される構造を有するエアロゲル複合体18を得た。
上記ゾル18を用いて、実施例1と同様にして、エアロゲル複合体付きフィルム状支持部材18、エアロゲル複合体付きシート状支持部材18、エアロゲル複合体付き箔状支持部材18及びエアロゲル複合体付き多孔質支持部材18を得た。
[湿潤ゲル、エアロゲル複合体]
上記で得られた湿潤ゲル17を、メタノール2500.0質量部に浸漬し、60℃で12時間かけて洗浄を行った。この洗浄操作を、新しいメタノールに交換しながら3回行った。次に、洗浄した湿潤ゲルを、2-プロパノール2500.0質量部に浸漬し、60℃で12時間かけて溶媒置換を行った。この溶媒置換操作を、新しい2-プロパノールに交換しながら3回行った。
[湿潤ゲル、エアロゲル複合体]
上記で得られた湿潤ゲル18を用いて、実施例19と同様にして上記一般式(3)、(6)及び(7)で表される構造を有するエアロゲル複合体20を得た。
[湿潤ゲル、エアロゲル複合体]
上記で得られた湿潤ゲル15を、メタノール2500.0質量部に浸漬し、60℃で12時間かけて洗浄を行った。この洗浄操作を、新しいメタノールに交換しながら3回行った。次に、洗浄された湿潤ゲルを、溶媒置換を行わず、常圧下にて、60℃で2時間、100℃で3時間乾燥し、その後さらに150℃で2時間乾燥することで、上記一般式(3)、(6)及び(7)で表される構造を有するエアロゲル複合体21を得た。
上記湿潤ゲル15を用いて得られた、湿潤ゲル付きの各支持部材を、メタノール100mLに浸漬し、60℃で2時間かけて洗浄を行った。次に、洗浄された湿潤ゲル付きの各支持部材を、常圧下にて、60℃で30分、100℃で1時間乾燥した。このようにして、エアロゲル複合体付きフィルム状支持部材21、エアロゲル複合体付きシート状支持部材21、エアロゲル複合体付き箔状支持部材21及びエアロゲル複合体付き多孔質支持部材21を得た。
[湿潤ゲル、エアロゲル複合体]
上記で得られた湿潤ゲル16を用いて、実施例21と同様にして上記一般式(2)、(6)及び(7)で表される構造を有するエアロゲル複合体22を得た。
上記湿潤ゲル16を用いて得られた、湿潤ゲル付きの各支持部材を用いて、実施例21と同様にして、エアロゲル複合体付きフィルム状支持部材22、エアロゲル複合体付きシート状支持部材22、エアロゲル複合体付き箔状支持部材22及びエアロゲル複合体付き多孔質支持部材22を得た。
[湿潤ゲル、エアロゲル]
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを100.0質量部加え、25℃で2時間反応させてゾル1Cを得た。得られたゾル1Cを60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル1Cを得た。その後、得られた湿潤ゲル1Cを用いて、実施例1と同様にしてエアロゲル1Cを得た。
上記ゾル1Cを用いて、実施例1と同様にして、エアロゲル付きフィルム状支持部材1C、エアロゲル付きシート状支持部材1C、エアロゲル付き箔状支持部材1C及びエアロゲル付き多孔質支持部材1Cを得た。
[湿潤ゲル、エアロゲル]
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを80.0質量部及びDMDMSを20.0質量部加え、25℃で2時間反応させてゾル2Cを得た。得られたゾル2Cを60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル2Cを得た。その後、得られた湿潤ゲル2Cを用いて、実施例1と同様にしてエアロゲル2Cを得た。
上記ゾル2Cを用いて、実施例1と同様にして、エアロゲル付きフィルム状支持部材2C、エアロゲル付きシート状支持部材2C、エアロゲル付き箔状支持部材2C及びエアロゲル付き多孔質支持部材2Cを得た。
[湿潤ゲル、エアロゲル]
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを70.0質量部及びDMDMSを30.0質量部加え、25℃で2時間反応させてゾル3Cを得た。得られたゾル3Cを60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル3Cを得た。その後、得られた湿潤ゲル3Cを用いて、実施例1と同様にしてエアロゲル3Cを得た。
上記ゾル3Cを用いて、実施例1と同様にして、エアロゲル付きフィルム状支持部材3C、エアロゲル付きシート状支持部材3C、エアロゲル付き箔状支持部材3C及びエアロゲル付き多孔質支持部材3Cを得た。
[湿潤ゲル、エアロゲル]
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにシリコン化合物としてMTMSを60.0質量部及びDMDMSを40.0質量部加え、25℃で2時間反応させてゾル4Cを得た。得られたゾル4Cを60℃でゲル化した後、80℃で24時間熟成して湿潤ゲル4Cを得た。その後、得られた湿潤ゲル4Cを用いて、実施例1と同様にして比較例エアロゲル4Cを得た。
上記ゾル4Cを用いて、実施例1と同様にして、エアロゲル付きフィルム状支持部材4C、エアロゲル付きシート状支持部材4C、エアロゲル付き箔状支持部材4C及びエアロゲル付き多孔質支持部材4Cを得た。
各実施例で得られた湿潤ゲル、エアロゲル複合体及びエアロゲル複合体付き支持部材、並びに各比較例で得られた湿潤ゲル、エアロゲル及びエアロゲル付き支持部材について、以下の条件に従って測定又は評価をした。湿潤ゲル生成工程におけるゲル化時間、メタノール置換ゲルの常圧乾燥におけるエアロゲル複合体及びエアロゲルの状態、並びにエアロゲル複合体及びエアロゲルの熱伝導率、圧縮弾性率、密度並びに気孔率の評価結果をまとめて表3に、エアロゲル複合体付き支持部材及びエアロゲル付き支持部材の180°屈曲試験の評価結果をまとめて表4に示す。
各実施例及び比較例で得られたゾル30mLを、100mLのPP製密閉容器に移し、測定サンプルとした。次に、60℃に設定した定温乾燥機「DVS402」(ヤマト科学株式会社製、製品名)を用い、測定サンプルを投入してからゲル化するまでの時間を計測した。
各実施例及び比較例で得られた湿潤ゲル30.0質量部を、メタノール150.0質量部に浸漬し、60℃で12時間かけて洗浄を行った。この洗浄操作を、新しいメタノールに交換しながら3回行った。次に、洗浄された湿潤ゲルを、刃角約20~25度の刃を用いて、100mm×100mm×100mmのサイズに加工し、乾燥前サンプルとした。得られた乾燥前サンプルを安全扉付き恒温器「SPH(H)-202」(エスペック株式会社製、製品名)を用い、60℃で2時間、100℃で3時間乾燥し、その後さらに150℃で2時間乾燥することで乾燥後サンプルを得た(特に溶媒蒸発速度等は制御していない)。ここで、サンプルの乾燥前後の体積収縮率SVを次式より求めた。そして、体積収縮率SVが5%以下であるときを「収縮なし」と評価し、5%以上であるときを「収縮」と評価した。
SV=(V0-V1)/V0×100
式中、V0は乾燥前サンプルの体積を示し、V1は乾燥後サンプルの体積を示す。
刃角約20~25度の刃を用いて、エアロゲル複合体及びエアロゲルを150mm×150mm×100mmのサイズに加工し、測定サンプルとした。次に、面の平行を確保するために、必要に応じて#1500以上の紙やすりで整形した。得られた測定サンプルを、熱伝導率測定前に、定温乾燥機「DVS402」(ヤマト科学株式会社製、製品名)を用いて、大気圧下、100℃で30分間乾燥した。次いで測定サンプルをデシケータ中に移し、25℃まで冷却した。これにより、熱伝導率測定用の測定サンプルを得た。
RS=N((TU-TL)/Q)-RO
式中、TUは測定サンプル上面温度を示し、TLは測定サンプル下面温度を示し、ROは上下界面の接触熱抵抗を示し、Qは熱流束計出力を示す。なお、Nは比例係数であり、較正試料を用いて予め求めておいた。
λ=d/RS
式中、dは測定サンプルの厚さを示す。
刃角約20~25度の刃を用いて、エアロゲル複合体及びエアロゲルを7.0mm角の立方体(サイコロ状)に加工し、測定サンプルとした。次に、面の平行を確保するために、必要に応じて#1500以上の紙やすりで測定サンプルを整形した。得られた測定サンプルを、測定前に、定温乾燥機「DVS402」(ヤマト科学株式会社製、製品名)を用いて、大気圧下、100℃で30分間乾燥した。次いで測定サンプルをデシケータ中に移し、25℃まで冷却した。これにより、圧縮弾性率測定用の測定サンプルを得た。
ε=Δd/d1
式中、Δdは負荷による測定サンプルの厚みの変位(mm)を示し、d1は負荷をかける前の測定サンプルの厚み(mm)を示す。
また、圧縮応力σ(MPa)は、次式より求めた。
σ=F/A
式中、Fは圧縮力(N)を示し、Aは負荷をかける前の測定サンプルの断面積(mm2)を示す。
E=(σ2-σ1)/(ε2-ε1)
式中、σ1は圧縮力が0.1Nにおいて測定される圧縮応力(MPa)を示し、σ2は圧縮力が0.2Nにおいて測定される圧縮応力(MPa)を示し、ε1は圧縮応力σ1において測定される圧縮ひずみを示し、ε2は圧縮応力σ2において測定される圧縮ひずみを示す。
エアロゲル複合体及びエアロゲルについての、3次元網目状に連続した細孔(通孔)の密度及び気孔率は、DIN66133に準じて水銀圧入法により測定した。なお、測定温度を室温(25℃)とし、測定装置としては、オートポアIV9520(株式会社島津製作所製、製品名)を用いた。
各実施例(実施例19及び20を除く)及び比較例で得られたエアロゲル複合体付き支持部材及びエアロゲル付き支持部材を50mm幅に加工し、JIS K5600-1に準じて、エアロゲル複合体層側のマンドレル試験を行った。マンドレル試験機としては、東洋精機製作所製のものを用いた。マンドレル半径1mmにおいて180°屈曲させた際のエアロゲル複合体及びエアロゲル層側のクラック及び/又は剥がれ発生の有無を目視にて評価した。そして、クラック及び/又は剥がれが発生しなかったものを「非破壊」、発生したものを「破壊」と評価した。
実施例15及び実施例16で得られたエアロゲル複合体付き箔状支持部材におけるエアロゲル複合体の表面をSEMにより観察した。図3は、実施例15で得られたエアロゲル複合体付き箔状支持部材におけるエアロゲル複合体の表面を、(a)1万倍、(b)5万倍、(c)20万倍及び(d)35万倍でそれぞれ観察したSEM画像である。図4は、実施例16で得られたエアロゲル複合体付き箔状支持部材におけるエアロゲル複合体の表面を、(a)1万倍、(b)5万倍、及び(c)20万倍でそれぞれ観察したSEM画像である。
(実施例23)
シリカ粒子含有原料としてPL-3L(扶桑化学工業株式会社製品名、平均一次粒子径35nmの球状コロイダルシリカが分散したゾル)を用いたこと以外は、実施例15と同様にしてエアロゲル複合体付き箔状支持部材を得た。
(実施例24)
シリカ粒子含有原料としてHL-3L(扶桑化学工業株式会社製品名、平均一次粒子径30nmの球状コロイダルシリカが分散したゾル)を用いたこと以外は、実施例15と同様にしてエアロゲル複合体付き箔状支持部材を得た。
Claims (13)
- エアロゲル成分及びシリカ粒子を含有するエアロゲル複合体。
- 前記エアロゲル成分及び前記シリカ粒子より形成された三次元網目骨格と、細孔とを有する、請求項1記載のエアロゲル複合体。
- 三次元網目骨格を構成する成分としてシリカ粒子を含有するエアロゲル複合体。
- シリカ粒子と、分子内に加水分解性の官能基を有するシリコン化合物及び該シリコン化合物の加水分解生成物からなる群より選択される少なくとも一種と、を含有するゾルから生成された湿潤ゲルを乾燥してなるエアロゲル複合体。
- シリカ粒子と、分子内に加水分解性の官能基を有するシリコン化合物及び該シリコン化合物の加水分解生成物からなる群より選択される少なくとも一種と、を含有するゾルから生成された湿潤ゲルを乾燥してなる、請求項1~3のいずれか一項記載のエアロゲル複合体。
- 前記ゾルが、分子内に反応性基を有するポリシロキサン化合物及び該ポリシロキサン化合物の加水分解生成物からなる群より選択される少なくとも一種をさらに含有する、請求項4又は5記載のエアロゲル複合体。
- 前記シリカ粒子の平均一次粒子径が1~500nmである、請求項1~6のいずれか一項記載のエアロゲル複合体。
- 前記シリカ粒子の形状が球状である、請求項1~7のいずれか一項記載のエアロゲル複合体。
- 前記シリカ粒子が非晶質シリカ粒子である、請求項1~8のいずれか一項記載のエアロゲル複合体。
- 前記非晶質シリカ粒子が溶融シリカ粒子、ヒュームドシリカ粒子及びコロイダルシリカ粒子からなる群より選択される少なくとも一種である、請求項9記載のエアロゲル複合体。
- 前記乾燥が、乾燥に用いられる溶媒の臨界点未満の温度及び大気圧下で行われる、請求項4又は5記載のエアロゲル複合体。
- 請求項1~11のいずれか一項記載のエアロゲル複合体と、該エアロゲル複合体を担持する支持部材と、を備えるエアロゲル複合体付き支持部材。
- 請求項1~11のいずれか一項記載のエアロゲル複合体を備える断熱材。
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- 2015-09-25 EP EP15843269.0A patent/EP3199493A4/en active Pending
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Cited By (13)
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JPWO2017010551A1 (ja) * | 2015-07-15 | 2018-02-22 | 日立化成株式会社 | エアロゲル複合材料 |
WO2017010551A1 (ja) * | 2015-07-15 | 2017-01-19 | 日立化成株式会社 | エアロゲル複合材料 |
US20190345362A1 (en) * | 2017-02-02 | 2019-11-14 | Hitachi Chemical Company, Ltd. | Treatment agent for treating particles, water-repellent particles and production method therefor, water-repellent layer, and penetration preventing structure |
US11905452B2 (en) | 2017-02-02 | 2024-02-20 | Resonac Corporation | Treatment agent for treating fibers, fibers and production method therefor, and fiber sheet and production method therefor |
KR102605765B1 (ko) | 2017-02-02 | 2023-11-27 | 가부시끼가이샤 레조낙 | 입자 처리용의 처리제, 발수성 입자 및 그 제조 방법, 발수층 그리고 침투 방지 구조체 |
KR20190113802A (ko) * | 2017-02-02 | 2019-10-08 | 히타치가세이가부시끼가이샤 | 입자 처리용의 처리제, 발수성 입자 및 그 제조 방법, 발수층 그리고 침투 방지 구조체 |
JP2018145331A (ja) * | 2017-03-07 | 2018-09-20 | 日立化成株式会社 | エアロゲルパウダー分散液 |
JP7024191B2 (ja) | 2017-03-07 | 2022-02-24 | 昭和電工マテリアルズ株式会社 | エアロゲルパウダー分散液 |
JP2018145332A (ja) * | 2017-03-07 | 2018-09-20 | 日立化成株式会社 | 樹脂組成物及び成形体 |
JPWO2018163354A1 (ja) * | 2017-03-09 | 2019-12-26 | 日立化成株式会社 | エアロゲル複合体の製造方法及びエアロゲル複合体 |
WO2018163354A1 (ja) * | 2017-03-09 | 2018-09-13 | 日立化成株式会社 | エアロゲル複合体の製造方法及びエアロゲル複合体 |
JP2020513049A (ja) * | 2017-04-13 | 2020-04-30 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 多孔質材料を製造する方法 |
US10824012B2 (en) | 2018-01-18 | 2020-11-03 | Samsung Display Co., Ltd. | Display device and method of manufacturing the same |
Also Published As
Publication number | Publication date |
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CN114702724A (zh) | 2022-07-05 |
EP3199493A1 (en) | 2017-08-02 |
TW202018014A (zh) | 2020-05-16 |
KR102425252B1 (ko) | 2022-07-25 |
MY179677A (en) | 2020-11-11 |
KR20170060027A (ko) | 2017-05-31 |
US20170283269A1 (en) | 2017-10-05 |
JP6428783B2 (ja) | 2018-11-28 |
SG10202003017RA (en) | 2020-05-28 |
US11780735B2 (en) | 2023-10-10 |
US10590001B2 (en) | 2020-03-17 |
JPWO2016047740A1 (ja) | 2017-07-20 |
CN107074563A (zh) | 2017-08-18 |
SG11201702422SA (en) | 2017-05-30 |
TWI737161B (zh) | 2021-08-21 |
EP3199493A4 (en) | 2018-03-07 |
TW201627404A (zh) | 2016-08-01 |
US20200148543A1 (en) | 2020-05-14 |
TWI736524B (zh) | 2021-08-21 |
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