WO2022163178A1 - Method for producing polysiloxane porous body, polysiloxane porous body, heat-insulating material, and heat-insulating container - Google Patents

Method for producing polysiloxane porous body, polysiloxane porous body, heat-insulating material, and heat-insulating container Download PDF

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WO2022163178A1
WO2022163178A1 PCT/JP2021/045943 JP2021045943W WO2022163178A1 WO 2022163178 A1 WO2022163178 A1 WO 2022163178A1 JP 2021045943 W JP2021045943 W JP 2021045943W WO 2022163178 A1 WO2022163178 A1 WO 2022163178A1
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mol
porous body
group
polysiloxane
polysiloxane porous
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PCT/JP2021/045943
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French (fr)
Japanese (ja)
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元 早瀬
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国立研究開発法人物質・材料研究機構
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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 a method for producing a polysiloxane porous body, a polysiloxane porous body, a heat insulating material, and a heat insulating container.
  • Patent Document 1 “Both of a bifunctional alkoxysilane and a trifunctional alkoxysilane or a trifunctional or higher alkoxysilane are used as starting materials, these silanes are copolymerized by a sol-gel reaction, Si- A method for producing an airgel or xerogel silicone monolith that forms a network of O bonds and undergoes phase separation and has continuous through channels and a silicone skeleton capable of dissolving chemical species.”
  • the present invention provides a method for producing a polysiloxane porous body that can produce a polysiloxane porous body having a skeleton composed of polysiloxane and having excellent flexibility without using a surfactant.
  • the task is to Another object of the present invention is to provide a polysiloxane porous body, a heat insulating material, and a heat insulating container.
  • the content of the tetraalkoxysilane is A method for producing a polysiloxane porous body, wherein the content is 10.5 to 20.0 mol%, and the content of the dimethyldialkoxysilane is 11.0 to 41.0 mol%.
  • [2] The method for producing a polysiloxane porous material according to [1], wherein the composition does not contain a surfactant.
  • [3] The method for producing a polysiloxane porous body according to [1] or [2], wherein the content of the dimethyldialkoxysilane is 38.0 mol% or less.
  • [4] The polysiloxane porous material according to [3], wherein the content of the methyltrialkoxysilane is 50.0 mol% or more and the content of the tetraalkoxysilane is 17.0 mol% or more. Production method.
  • [5] The method for producing a polysiloxane porous body according to [3], wherein the content of the methyltrialkoxysilane is 67.0 mol % or more.
  • [6] The method for producing a polysiloxane porous body according to any one of [1] to [5], wherein the polysiloxane porous body has a bulk density of 0.300 gcm ⁇ 3 or less.
  • [7] The method for producing a polysiloxane porous material according to any one of [1] to [6], which has a thermal conductivity of 0.0400 W/(m ⁇ K) or less at 20°C.
  • the content of the tetraalkoxysilane is 10.5 to 20.0 mol%.
  • a method for producing a polysiloxane porous body that can produce a polysiloxane porous body having a skeleton composed of polysiloxane and having excellent flexibility without using a surfactant.
  • the present invention can also provide a polysiloxane porous body, a heat insulating material, and a heat insulating container.
  • Fig. 3 is a ternary diagram showing the content of each silicon alkoxide component in the composition.
  • 1 is a perspective view showing the overall configuration of a heat insulating container 1 according to one embodiment of the present invention; FIG. It is a sectional view of a heat insulating container.
  • Fig. 3 is an exploded cross-sectional view of the heat insulating container; It is a perspective view of a heat insulating material.
  • FIG. 4 is a diagram for explaining a method of attaching a heat insulating material to the heat insulating container; It is a modification of the heat insulating container.
  • 1 is a ternary diagram plotted with each composition of the examples.
  • co-continuous structure means that when a cut surface of a member (polysiloxane porous body) is observed with a scanning electron microscope, a skeleton phase containing polysiloxane as a main component and voids are continuous, Also, it means a state in which they are three-dimensionally intertwined with each other.
  • macropores as used herein means pores with a pore diameter (pore diameter) of 50 nm or more according to the proposal by IUPAC.
  • the pore size and average pore size of the pores are determined by image analysis of electron microscopic images.
  • TEAS, MTAS and DMDAS may be collectively simply referred to as "silicon alkoxide”.
  • the present inventor has investigated a method for producing a silicone skeleton monolith having excellent flexibility without using a surfactant. Synthesis of a silicone skeleton monolith proceeds through a so-called sol-gel reaction. Therefore, a composition containing a polyfunctional silicon alkoxide having a hydrolyzable group is prepared, and the polycondensate of the hydrolysis product of the silicon alkoxide in the composition, that is, polysiloxane, which is the skeleton phase of the gel, is sequentially increased. It is manufactured by letting
  • the skeleton phase and the solution phase are each continuous three-dimensional.
  • a co-continuous structure having a mesh structure and being entangled with each other is formed.
  • phase separation control agent phase separation control agent
  • phase separation behavior can be controlled, viscoelastic phase separation can be caused, and a polysiloxane porous body having excellent flexibility can be obtained.
  • the method for producing the polysiloxane porous body will be described in detail below.
  • the tetraalkoxysilane used in this production method is a compound represented by the formula 1: Si—(OR 1 ) 4 where R 1 is an alkyl group (a plurality of R 1s in the molecule may be the same or different). but preferably identical).
  • the alkyl group for R 1 may be linear, branched, or cyclic. Alkyl groups are preferred. Although the number of carbon atoms in R 1 is not particularly limited, it is preferably 1 to 10 because the alcohol produced by hydrolytic condensation has superior hydrophilicity.
  • linear or branched alkyl groups having 1 to 10 carbon atoms include the following groups. methyl group with 1 carbon atom; ethyl group with 2 carbon atoms; propyl group with 3 carbon atoms, isopropyl group; butyl group with 4 carbon atoms, isobutyl group, tert-butyl group, sec-butyl Group; pentyl group having 5 carbon atoms, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group; carbon number is six hexyl groups, 1-methylpentyl groups, 2-methylpentyl groups, 3-methylpentyl groups, 4-methylpentyl groups, 1,1-dimethylbutyl groups, 1,2-dimethylbutyl groups, 1,3 -dimethylbutyl group, 1,4-dimethylbutyl group, 2,3-dimethylbut
  • the cyclic alkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
  • the cyclic alkenyl group a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, a cyclohexadienyl group, a cycloheptenyl group, a cycloheptadienyl group, a cyclooctenyl group, and a cyclo octadienyl group and the like.
  • a cyclic alkynyl group includes a cycloalkenyl group; a cyclooctynyl group, a cyclononynyl group, a cyclodecynyl group, a cyclodecadiynyl group, and the like.
  • TEAS examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, and the like. From the viewpoint of cost, tetramethoxysilane (TMOS) is preferred.
  • TMOS tetramethoxysilane
  • MTAS Metaltrialkoxysilane
  • the methyltrialkoxysilane used in this production method is a compound represented by the formula 2: CH 3 —Si—(OR 2 ) 3 where R 2 is an alkyl group (a plurality of R 2 in the molecule are the same may be different, but are preferably the same).
  • the alkyl group for R2 has the same meaning as the alkyl group for R1 , and the preferred forms are also the same.
  • MTAS examples include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, and methyltributoxysilane, and methyltrimethoxysilane (MTMS) is preferred.
  • the dimethyldialkoxysilane used in this production method is a compound represented by the formula 3: (CH 3 ) 2 —Si—(OR 3 ) 2 where R 3 is an alkyl group (a plurality of R 3 may be the same or different, but are preferably the same).
  • the alkyl group for R3 has the same definition as the alkyl group for R1 , and the preferred forms are also the same.
  • DMDAS examples include dimethyldimethoxysilane, diethoxydimethylsilane, and the like, with dimethyldimethoxysilane (DMDMS) being preferred.
  • the manufacturing method includes preparing a composition comprising TEAS, MTAS, DMDAS, and water, gelling to form a gel, and drying the resulting gel.
  • the content of TEAS in the composition is 10.5 to 20.0 mol% when the total of TEAS, MTAS and DMDAS is 100 mol% (10.5 mol% ⁇ TEAS ⁇ 20 mol% .0 mol %). If TEAS is less than 10.5 mol % or more than 20.0 mol %, a polysiloxane porous body having excellent flexibility cannot be obtained in a system that does not use a surfactant.
  • the content of DMDAS is 11.0 to 41.0 mol% when the total of TEAS, MTAS and DMDAS is 100 mol% (11.0 mol% ⁇ DMDAS ⁇ 41.0 mol% ). If DMDAS is less than 11.0 mol % or more than 41.0 mol %, a polysiloxane porous body having excellent flexibility cannot be obtained in a system that does not use a surfactant.
  • the content of MTAS is 39.0 to 78.5 mol% when the total of TEAS, MTAS and DMDAS is 100 mol% (39.0 mol% ⁇ MTAS ⁇ 78.5 mol% ).
  • the content of silicon alkoxide in the present composition is 10.5 mol% ⁇ TEAS ⁇ 20.0 mol%, 11.0 mol% ⁇ DMDAS ⁇ 41.0 mol%, and 39.0 mol% ⁇ MTAS ⁇ 78.5 mol%, is.
  • FIG. 1 is a ternary diagram showing the content of each silicon alkoxide component in the composition. Of these, the shaded portion in FIG. 1 satisfies the above numerical range.
  • the content of DMDAS in the composition is preferably 38.0 mol % or less from the viewpoint that the resulting polysiloxane porous body has superior heat insulating properties (lower thermal conductivity). That is, from the viewpoint of obtaining a polysiloxane porous body having superior heat insulating properties, the silicon alkoxide content in the composition is preferably within the following ranges. 10.5 mol% ⁇ TEAS ⁇ 20.0 mol%, 11.0 mol% ⁇ DMDAS ⁇ 38.0 mol%, and 39.0 mol% ⁇ MTAS ⁇ 78.5 mol%
  • the content of DMDAS is 38.0 mol% or less and the content of MTAS is 50.0 mol% or less, Moreover, it is more preferable that the content of TEAS is 17.0 mol % or more. That is, from the viewpoint of obtaining a polysiloxane porous body having even better heat insulating properties, it is more preferable that the content of the silicon alkoxide in the composition is within the following ranges.
  • DMDAS is preferably 30.0 mol % or more. That is, it is preferable that 30.0 mol % ⁇ DMDAS ⁇ 38.0 mol %.
  • a polysiloxane porous body having a further excellent heat insulating property when the content of DMDAS is 38.0 mol% or less and the content of MTAS is 67.0 mol% or more is obtained. 10.5 mol% ⁇ TEAS ⁇ 20.0 mol%, 11.0 mol% ⁇ DMDAS ⁇ 38.0 mol%, and 67.0 mol% ⁇ MTAS ⁇ 78.5 mol%
  • the composition contains water. Although the content of water in the composition is not particularly limited, it is preferably 0.1 to 90% by mass.
  • the composition can be prepared by mixing the ingredients previously described. Among them, the content of the solvent is 50% by mass when the total mass of the composition is 100% by mass, from the viewpoint that the obtained polysiloxane porous body has better heat insulation (lower thermal conductivity). 55% by mass or more is more preferable, and 57% by mass or more is even more preferable.
  • the composition preferably does not contain surfactants.
  • surfactant-free it is meant that the surfactant content is less than 0.001 mol per 1 mol of silicon (total) of TEAS, MTAS and DMDAS. , is preferably 0.0001 mol or less, more preferably 0.00001 mol or less.
  • Surfactants include cationic, anionic, amphoteric, and nonionic.
  • anionic surfactants include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid, lauryl sulfate, polyoxyethylene lauryl sulfate, de Decenesulfonic acid, tetradecenesulfonic acid, hexadecenesulfonic acid, hydroxydodecanesulfonic acid, hydroxytetradecanesulfonic acid, hydroxyhexadecanesulfonic acid, and their sodium salts, potassium salts, ammonium salts, and triethanolamine salts. be done.
  • cationic surfactants include octyltrimethylammonium hydroxide, lauryltrimethylammonium hydroxide, stearyltrimethylammonium hydroxide, dioctyldimethylammonium hydroxide, distearyldimethylammonium hydroxide, lauryltrimethylammonium chloride, and stearyltrimethylammonium chloride. , cetyltrimethylammonium chloride, dicocoyldimethylammonium chloride, distearyldimethylammonium chloride, benzalkonium chloride, and stearyldimethylbenzylammonium chloride.
  • nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, and polyoxyethylene sorbitol fatty acid ester. , polyethylene glycol, polypropylene glycol, and diethylene glycol.
  • Amphoteric surfactants include, for example, amino acid-type and betaic acid-type surfactants.
  • composition may contain other ingredients within the scope of the effects of the present invention.
  • Other components include, for example, acids and bases.
  • the composition contains an acid.
  • the acid hydrolyzes the alkoxysilane and catalyzes the curing reaction.
  • alkoxysilane is hydrolyzed in the system to produce hydrolysis products, polycondensation reactions occur one after another in order.
  • Acid hydrolysis proceeds electrophilically with H 3 O + . That is, H 3 O + attacks the oxygen atom of the alkoxy group to generate -Si-OH and alcohol. This reaction has no effect of steric hindrance, hydrolysis and polycondensation proceed successively, and linear polysiloxane is easily synthesized.
  • the acid may be an inorganic acid or an organic acid.
  • inorganic acid hydrochloric acid, sulfuric acid, etc. can be used.
  • organic acid formic acid, acetic acid, propionic acid, oxalic acid, citric acid, and the like can be used, and acetic acid is preferable because the hydrolysis reaction is easier to control.
  • the content of the acid in the composition is not particularly limited, but since the polysiloxane porous body has better shape stability and flexibility, the content of water in the composition is 1 L. is preferably 1 to 100 mmol, more preferably 5 to 10 mmol.
  • the composition contains a base.
  • the base hydrolyzes the alkoxysilane and catalyzes the curing reaction. Hydrolysis with a base proceeds nucleophilically with OH- . That is, OH- directly attacks a silicon atom to generate RO- ( R is an organic group). Although this reaction is initially difficult to proceed due to the effects of steric hindrance and the like, once it proceeds, the steric hindrance is alleviated and the reaction tends to proceed rapidly. As a result, the number of hydroxy groups that contribute to polycondensation increases, so branched polysiloxanes are easily synthesized.
  • the base is not particularly limited, but alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide, and barium hydroxide. substances; alkali metal carbonates such as potassium carbonate and sodium carbonate; ammonia; amines such as monomethylamine, dimethylamine, triethylamine, monoethylamine, diethylamine, ethylenediamine, monoethanolamine, diethanolamine, and triethanolamine mentioned.
  • alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide
  • alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • alkali metal carbonates such as potassium carbonate and sodium carbonate
  • ammonia amines such as monomethylamine, dimethylamine, triethylamine, monoethylamine, diethylamine, ethylenediamine
  • Substances that produce basic substances by decomposition reaction may also be used, and examples of such substances include urea and hexamine. Urea is preferred because it is easy to remove.
  • the content of the base in the composition is not particularly limited, it is preferably from 1 mM to 15M in that the polysiloxane porous body has superior shape stability and flexibility.
  • the polysiloxane porous material is obtained by hydrolyzing silicon alkoxide by a sol-gel method using a composition obtained by mixing the components already described, and hydrolyzing the silicon alkoxide obtained by the hydrolysis.
  • Polycondensation and phase separation of the polycondensate (polysiloxane) obtained by polycondensation and the solution system containing unreacted silicon alkoxide and hydrolysis products are performed in parallel to form a skeleton phase and a solution phase. including a step of forming a gel (gelation step).
  • the skeleton phase of the gel formed in the gelling process is rich in polycondensates of the hydrolysis products of the silicon alkoxides.
  • the solution phase is rich in the solvent of the composition and the content of the polycondensate in the solution phase is relatively low compared to the content in the skeleton phase.
  • Phase separation is phase separation that proceeds simultaneously with hydrolysis of silicon alkoxide and polycondensation of hydrolysis products, typically viscoelastic phase separation.
  • the skeletal phase and solution phase generated through such a phase separation process each have a continuous three-dimensional network structure and are entangled with each other.
  • the gel formed in the gelation process has a co-continuous structure of the skeleton phase and the solution phase.
  • the polymer constituting the skeleton phase is a polysiloxane having a network of siloxane bonds (--Si--O--Si--) formed by polycondensation of the hydrolysis product of the silicon alkoxide by a sol-gel reaction. be. That is, the gel formed in the gelation step is polysiloxane gel.
  • the gelation process proceeds by mixing each component and preparing a composition.
  • the composition may be heated.
  • the heating conditions are not particularly limited, 40 to 100° C. is generally preferred, and the heating time is preferably 2 to 48 hours.
  • the gel obtained by the gelation process is a wet gel of polysiloxane.
  • the drying step is a step of drying the wet gel to obtain a polysiloxane porous body.
  • the drying method is not particularly limited, but includes a method of holding at room temperature to 120° C. for 1 to 24 hours.
  • a silicon alkoxide having a hydrolyzable group in its molecule forms a network of siloxane bonds through polycondensation of hydrolysis products by a sol-gel reaction. Since the present composition uses di-, tri-, and tetra-functional alkoxysilanes in combination, a rigid network generated by tri- and tetra-functional alkoxysilanes and a planar network with a high degree of freedom generated by di-functional alkoxysilanes will result in a flexible connection. As a result, the obtained polysiloxane porous material exhibits flexibility even after drying while having a skeleton composed of polysiloxane.
  • the present production method may have other steps than those described above as long as the effects of the present invention are not impaired.
  • Other steps include, for example, a step of heating and dehydrating the polysiloxane porous body.
  • the heating temperature at this time is not particularly limited, it is preferably higher than 200°C. If silanol (Si—OH) remains in the polysiloxane porous material, it can be dehydrated by heating. Since the polysiloxane porous material has excellent heat resistance, this step does not impair its flexibility.
  • the polysiloxane porous material prepared by the above method has a co-continuous structure of a skeleton composed of polysiloxane and macropores.
  • the polysiloxane constituting the skeleton is polysiloxane formed by hydrolysis of these silicon alkoxides and polycondensation of the hydrolysis products in the composition containing TEAS, MTAS and DMDAS.
  • it is a monolithic macroporous member of a silicone composition whose skeleton is formed by viscoelastic phase separation that accompanies the polycondensation reaction of a given silicon alkoxide in an aqueous solution.
  • the degree of flexibility is, for example, 100 kPa or less in terms of Young's modulus. Due to such high flexibility and light scattering due to the presence of macropores, the polysiloxane porous material was named "marshmallow gel" by the present inventors because it is white in an uncolored state.
  • the above polysiloxane porous material has macropores with a uniform pore size because macropores having a co-continuous structure with the skeleton are formed through a sol-gel reaction combined with a phase separation process.
  • Such a structure is completely different from the structure of a porous body obtained through a foaming process using a foaming agent (in such a porous body, a large number of independent pores are formed by foaming).
  • the average diameter of the skeleton is, for example, preferably 500 nm or more and preferably less than 10 ⁇ m.
  • the average pore size of macropores is, for example, 500 nm to 200 ⁇ m.
  • the average pore diameter of the pores of the polysiloxane porous body is preferably 1 ⁇ m or more, and preferably less than 100 ⁇ m.
  • the skeleton diameter and average pore diameter of the polysiloxane porous material can be determined by image analysis of electron microscope observation images.
  • the porosity of the polysiloxane porous material is preferably, for example, 75 to 98% as measured by a laser confocal microscope.
  • the above-mentioned polysiloxane porous body is stable in a wide temperature range because its skeleton is composed of polysiloxane. For example, it can retain its flexibility from liquid nitrogen temperature ( ⁇ 196° C.) to the temperature at which polysiloxane decomposes (approximately 320° C.).
  • the present polysiloxane porous material has both excellent heat resistance and excellent heat insulating properties, and although there are no particular restrictions on the thermal conductivity, the thermal conductivity at 20° C. (atmospheric pressure, in air) is 0.5. 0400 W/(m ⁇ K) or less is preferable, 0.0350 W/(m ⁇ K) or less is more preferable, and 0.0330 W/(m ⁇ K) or less is even more preferable.
  • the lower limit is not particularly limited, but generally 0.0120 W/(m ⁇ K) or more is preferable.
  • the thermal conductivity is measured by the method described in Examples below.
  • the bulk density of the present polysiloxane porous material is not particularly limited, but is preferably 0.300 gcm -3 (g/cm 3 ) or less, more preferably 0.200 gcm -3 or less, and even more preferably 0.110 gcm -3 or less. . Although the lower limit is not particularly limited, 0.010 gcm ⁇ 3 or more is generally preferred.
  • the present polysiloxane porous body has excellent bending resistance.
  • a polysiloxane porous body having a thickness of 5 mm is prepared and wound around a cylinder (rod) having a diameter of 10 mm, it is preferable that no cracks occur.
  • the present polysiloxane porous body has excellent flexibility, and a flat polysiloxane porous body is prepared and uniaxially compressed to 80% of the total height (to 20% of the original size).
  • the compression set remaining after unloading is preferably 10% or less, more preferably 8% or less, and even more preferably 5% or less.
  • the present polysiloxane porous body undergoes little change in thermal conductivity even when it is deformed by compression from the outside.
  • the rate of change in thermal conductivity is not particularly limited.
  • the rate of change in thermal conductivity compared is preferably 10.0% or less, more preferably 6.0% or less.
  • the rate of change in thermal conductivity is preferably 10.0% or less, more preferably 6.0% or less, over the entire compressibility range of 0 to 60%.
  • the rate of change in thermal conductivity is a value obtained by rounding off to the second decimal place.
  • the present polysiloxane porous body has excellent flexibility, excellent heat resistance, excellent heat insulating properties, etc., and can be used as a heat insulating material and the like.
  • it can be used as a liquid nitrogen adsorbent that adsorbs and retains liquid nitrogen because it retains its flexibility even at the temperature of liquid nitrogen.
  • the present polysiloxane porous body has liquid repellency and antifouling properties, and can be used as a liquid repellent substrate or the like. It can also be used as a water/oil separation medium, liposome preparation, and sound and vibration insulating material. Furthermore, by crushing, it can be used as an additive for cosmetics, a resin filler (filler), a reflective material, and the like.
  • a heat insulating container according to an embodiment of the present invention is a heat insulating container provided with a heat insulating material containing the present polysiloxane porous material.
  • FIG. 2 is a perspective view showing the overall configuration of the heat insulating container 1 according to one embodiment of the present invention.
  • FIG. 3 is a cross-sectional view of the heat insulating container 1.
  • FIG. 4 is an exploded sectional view of the heat insulating container 1.
  • FIG. 3 and 4 are cross-sectional views taken along a plane parallel to the XY plane at the radial center of the heat insulating container 1.
  • the heat insulating container 1 includes a housing 10, a container body 20, a heat insulating material storage portion 30, a support member 40, a heat insulating material 50 (see FIG. 5), and a container opening/closing portion 60.
  • the heat-retaining container 1 is a heat-retaining container used for transporting goods that require temperature control, such as pharmaceuticals for humans and animals, quasi-drugs, food and drink, and test and research reagents.
  • the heat insulating container 1 is formed in a cylindrical shape as a whole.
  • the housing 10 is the outermost member of the heat insulating container 1, and as shown in FIG. 3, has a concave cross section parallel to the XY plane.
  • the housing 10 is provided with a vacuum heat insulating layer 13 between the outer surface 11 and the inner surface 12 .
  • the vacuum heat insulating layer 13 is a layer filled with gas having a pressure lower than atmospheric pressure.
  • the vacuum heat insulating layer 13 communicates with the radial (X direction) side surface of the housing 10 and the lower (Y2 side) bottom surface of the housing 10 . That is, the vacuum heat insulating layer 13 is formed to have a concave shape in the housing 10 except for the container opening/closing part 60 side.
  • the housing 10 is made of, for example, a metal member such as aluminum and stainless steel.
  • the outer surface 11 of the housing 10 is provided with a threaded portion 11s at the end portion on the upper side (Y1 side).
  • the threaded portion 11s is a male screw that engages with a threaded portion 61s of a container opening/closing portion 60 (opening/closing portion main body 61), which will be described later.
  • the container body 20 is a member provided inside the inner surface 12 of the housing 10, and as shown in FIG. 3, is formed so that the cross section parallel to the XY plane has a concave shape. An object to be kept warm (not shown) is accommodated inside the container body 20 .
  • the outer diameter of container body 20 is smaller than the inner diameter of housing 10 , and gap g ⁇ b>1 is formed between inner surface 12 of housing 10 and outer surface 22 of container body 20 .
  • a heat insulating material housing portion 30 (described later) is provided in the space of the gap g1.
  • the heat insulating container 1 does not have to have this container body 20 when a heat insulating material, which will be described later, is used as a cushioning material.
  • the present polysiloxane porous material is characterized in that it does not lose its flexibility even when impregnated with liquid nitrogen, and does not lose its buffering properties even at extremely low temperatures. Therefore, in the form without the container main body 20, the heat insulating material has two functions of heat insulation and cushioning. A heat insulating container of this form will be described later.
  • the container body 20 is made of a metal member such as aluminum or stainless steel.
  • the container body 20 is supported by a support member 40 inside the housing 10 .
  • the support member 40 is a member that connects the bottom surface 14 of the housing 10 and the bottom surface 21 of the container body 20 .
  • a gap g2 is formed between the bottom surface 14 of the housing 10 and the bottom surface 21 of the container body 20 by supporting the container body 20 with the support member 40 .
  • the heat insulating material is not arranged in the space of the gap g2, but when the support member 40 is arranged on the side surface of the container body 20, the heat insulating material 50 can be arranged in the space of the gap g2.
  • FIG. 3 an example in which two support members 40 are provided along the radial direction (X direction) of the housing 10 is shown. is set to
  • the heat insulating material housing portion 30 is a cylindrical space provided between the housing 10 and the container body 20.
  • a heat insulator 50 is detachably stored in the heat insulator storage portion 30 . 2 to 4 do not show the heat insulating material 50.
  • FIG. A configuration of the heat insulating material 50 will be described later.
  • the container opening/closing part 60 is a member that opens or closes the opening 23 of the container body 20 and the opening 31 of the heat insulating material storage part 30, as shown in FIG.
  • the container opening/closing part 60 is composed of an opening/closing part main body 61 .
  • Each part constituting the container opening/closing part 60 may be made of a metal member like the housing 10, or may be made of a resin material such as plastic.
  • the opening/closing unit main body 61 is a member detachably attached to the housing 10, and is formed to have a substantially convex cross section.
  • a screw portion 61s is provided on the inner peripheral surface of the opening/closing portion main body 61 on the Y2 side, which is the rear surface side.
  • the threaded portion 61s is a female thread that engages with the threaded portion 11s provided on the housing 10 .
  • the opening/closing part main body 61 can be attached to the housing 10 by rotating the opening/closing part main body 61 so that the screw part 61s of the opening/closing part main body 61 is engaged with the screw part 11s of the housing 10 .
  • the opening/closing unit main body 61 By attaching the opening/closing unit main body 61 to the housing 10, the opening 23 of the container main body 20 and the opening 31 of the heat insulating material storage unit 30 are closed as shown in FIG. 4, the opening 23 of the container body 20 and the opening 31 of the heat insulating material storage part 30 are opened by removing the opening/closing part main body 61 from the housing 10. As shown in FIG.
  • the heat insulating material contains the present polysiloxane porous body. Since the present polysiloxane porous material has excellent heat insulating properties, the heat insulating container 1 provided with the present polysiloxane porous material has excellent heat retaining performance.
  • the heat insulating material may further contain a liquid medium.
  • This polysiloxane porous material has excellent temperature stability and continuous macropores, and can easily adjust the temperature inside the container by impregnating it with a heated or cooled liquid medium. can be controlled to Examples of liquid media include liquid nitrogen.
  • FIG. 5 is a perspective view showing how the heat insulating material 50 is used.
  • the heat insulating material 50 includes the present polysiloxane porous body and has a cylindrical shape.
  • the outer diameter D1 and the inner diameter D2 of the heat insulating material 50 are set so that the heat insulating material 50 can be accommodated in the gap g1 (see FIG. 3) of the heat insulating material accommodating portion 30.
  • a gap may be formed between the heat insulating material 50 and the heat insulating material housing portion 30 .
  • FIG. 6A and 6B are diagrams for explaining a method of attaching the heat insulating material 50 to the heat insulating container 1.
  • FIG. In order to store the heat insulating material 50 in the heat insulating material housing portion 30 (housing 10), as shown in FIG. do. Then, the heat insulating material 50 is inserted through the opening 31 of the heat insulating material housing portion 30 .
  • the container body 20 is supported by a support member 40 that connects the bottom surface 14 of the housing 10 and the bottom surface 21 of the container body 20 . Therefore, the heat insulating container 1 can more stably hold the container body 20 inside the housing 10 .
  • Fig. 7 is a modification of the heat insulating container.
  • the heat insulating container 2 does not have the container body 20 that the heat insulating container 1 has, but has a cylindrical heat insulating material 50 having a bottom.
  • the heat insulating object is held in direct contact with the heat insulating material 50.
  • the heat insulating material 50 has excellent flexibility and thus functions as a cushioning material.
  • the thickness of the heat insulating material 50 is larger than that of the heat insulating container 1. - ⁇ As a result, not only is the heat retaining property higher, but also the cushioning performance of the heat retaining material 50 is enhanced.
  • the thickness of the heat-retaining container 2 may be determined as appropriate, but may be adjusted, for example, so that the object to be heat-retained fits tightly. That is, if the object to be kept warm is cylindrical, the thickness of the heat insulating material 50 should be adjusted so that the cylinder fits perfectly.
  • the heat insulating material 50 is impregnated with liquid nitrogen or the like, the inside of the heat insulating container 2 can be maintained at a low temperature without losing the buffering function of the heat insulating material 50, which is preferable for transporting medicines and the like that need to be transported at low temperatures. can be used.
  • the present polysiloxane porous body has excellent flexibility and little change in thermal conductivity due to compression. It has the characteristic that excellent heat retention effect (insulation effect) can be obtained even when used in .
  • TMOS tetramethoxysilane
  • MTMS methyltrimethoxysilane
  • DDMS dimethyldimethoxysilane
  • the composition was transferred to an airtight container (gel type) and kept at 80°C for 24 hours for reaction (gelation/aging).
  • the resulting gel was removed from the mold, washed once with 5 or more volumes of pure water and twice with industrial alcohol for at least 6 hours each, and then evaporated to dryness at 60°C to obtain a cured product in a dry state. (Polysiloxane porous body) was obtained.
  • FIG. 8 plots each composition in a ternary diagram. Those for which the above evaluations were all "A” (marshmallow gel) were designated as “ ⁇ (middle black circle)”, and those for which evaluation 1 was “A” and evaluation 2 was “B” were designated as “ ⁇ (middle white) Yen)”, and the evaluation 1 was “B” was designated as “ ⁇ (white triangle)”.
  • the polysiloxane porous material obtained from the composition indicated by " ⁇ ” in FIG. 8 is a monolithic macroporous member ( marshmallow gel). On the other hand, " ⁇ " and “ ⁇ ” were not marshmallow gels.
  • Thermal conductivity was measured by a heat flow meter method (ASTM C518) using "small" of "HFM446 Lambda” from NETZSCH. The temperature of the upper plate was set at 25° C. (high temperature side) and the temperature of the lower plate was set at 15° C. (low temperature side), and the thermal conductivity was measured while the sample was sandwiched between the two plates and a compressive stress was applied. The test was conducted at 20°C, which is the intermediate temperature between the upper and lower plates. The sample was a marshmallow gel panel with a thickness of about 10 mm (size: 110 mm x 110 mm).
  • the content of silicon alkoxide is 10.5 mol% ⁇ TEAS ⁇ 20.0 mol%, and It was found that using the compositions of Examples 1-9, where 11.0 mol % ⁇ DMDAS ⁇ 41.0 mol %, yields homogeneous polysiloxane porous bodies with excellent flexibility. On the other hand, when the compositions of Examples 10 to 25, which are outside the above range, are used, a homogeneous polysiloxane porous body (dry body) cannot be obtained, or even if a polysiloxane porous body is obtained, it is co-continuous. macropores and did not have the desired flexibility (no marshmallow gel was obtained).
  • the content of silicon alkoxide is 10.5 mol% ⁇ TEAS ⁇ 20.0 mol%, 11.0 mol% ⁇ DMDAS ⁇ 38.0 mol%, and 39.0 mol% ⁇ MTAS ⁇ 78.5 mol%
  • the polysiloxane porous body of the composition of Example 2 which is within the above range, has a lower thermal conductivity (higher heat insulation) than the polysiloxane porous body of the composition of Example 1, which is outside the above range.
  • the content of silicon alkoxide is 17.0 mol% ⁇ TEAS ⁇ 20.0 mol%, 11.0 mol% ⁇ DMDAS ⁇ 38.0 mol%, and 39.0 mol% ⁇ MTAS ⁇ 50 mol%
  • the polysiloxane porous body of the composition of Example 2 which is within the range of, has a lower thermal conductivity (higher heat insulation) than the polysiloxane porous body of the composition of Example 4, which is outside the above range. It turns out that
  • the content of silicon alkoxide is 10.5 mol% ⁇ TEAS ⁇ 20.0 mol%, 11.0 mol% ⁇ DMDAS ⁇ 38.0 mol%, and 67.0 mol% ⁇ MTAS ⁇ 78.5 mol%
  • the polysiloxane porous body of the composition of Example 5 which is within the range of, has a lower thermal conductivity (higher heat insulation) than the polysiloxane porous body of the composition of Example 4, which is outside the above range. It turns out that
  • a polysiloxane porous body having excellent flexibility can be obtained without using a surfactant.
  • a surfactant Conventionally, it has been considered essential to use a surfactant in order to obtain a similar polysiloxane porous material, and its removal requires washing with a large amount of organic solvent, which has a large environmental impact.
  • This manufacturing method solves the above problems.
  • the polysiloxane porous material obtained by this production method has excellent flexibility, excellent heat resistance, excellent heat insulating properties, etc., and can be used as a heat insulating material.
  • it can be used as a liquid nitrogen adsorbent that adsorbs and retains liquid nitrogen because it retains its flexibility even at the temperature of liquid nitrogen.
  • the present polysiloxane porous body has liquid repellency and antifouling properties, and can be used as a liquid repellent substrate or the like. It can also be used as a water/oil separation medium, liposome preparation, and sound and vibration insulating material. Furthermore, by crushing, it can be used as an additive for cosmetics, a resin filler (filler), a reflective material, and the like.
  • Thermal insulation container 10 Housing 11: Outer surface 11s: Threaded portion 12: Inner surface 13: Vacuum insulation layer 14: Bottom surface 20: Container main body 21: Bottom surface 22: Outer surface 23: Opening 30: Heat insulating material storage Portion 31: opening 40: support member 50: heat insulating material 60: container opening/closing portion 61: opening/closing portion main body 61s: screw portion

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Abstract

The present invention provides a method for producing a polysiloxane porous body, the method making it possible to produce a polysiloxane porous body having exceptional flexibility. The production method according to the present invention includes: preparing a composition including a tetraalkoxysilane, a methyl trialkoxysilane, a dimethyldialkoxysilane, and water, and gelling the composition to form a gel; and drying the gel to obtain a polysiloxane porous body. When the total of the tetraalkoxysilane content, the methyl trialkoxysilane content, and the dimethyldialkoxysilane content in the composition is taken as 100 mol%, the tetraalkoxysilane content is 10.5-20.0 mol%, and the dimethyldialkoxysilane content is 11.0-41.0 mol%.

Description

ポリシロキサン多孔体の製造方法、ポリシロキサン多孔体、保温材、及び、保温容器Method for producing polysiloxane porous body, polysiloxane porous body, heat insulating material, and heat insulating container
　本発明は、ポリシロキサン多孔体の製造方法、ポリシロキサン多孔体、保温材、及び、保温容器に関する。 The present invention relates to a method for producing a polysiloxane porous body, a polysiloxane porous body, a heat insulating material, and a heat insulating container.
　ポリシロキサンから構成される骨格を有しながら、柔軟性を有するマクロ多孔体が知られている。特許文献１には、「二官能基のアルコキシシランと、三官能基のアルコキシシラン又は三官能以上のアルコキシシラン類との両方を出発原料とし、ゾルゲル反応によりこれらのシランを共重合させ、Ｓｉ－Ｏ結合のネットワークを形成させると共に相分離を行い、連続貫通流路と化学種を溶解できるシリコーン骨格とを有するエアロゲル又はキセロゲルのシリコーン製モノリス体の製造方法。」が記載されている。 A macroporous body that has flexibility while having a skeleton composed of polysiloxane is known. In Patent Document 1, "Both of a bifunctional alkoxysilane and a trifunctional alkoxysilane or a trifunctional or higher alkoxysilane are used as starting materials, these silanes are copolymerized by a sol-gel reaction, Si- A method for producing an airgel or xerogel silicone monolith that forms a network of O bonds and undergoes phase separation and has continuous through channels and a silicone skeleton capable of dissolving chemical species.".
特開２０１４－６１４５７号公報JP 2014-61457 A
　特許文献１に記載された製造方法によれば、優れた柔軟性を有するシリコーン製モノリスが製造できるものの、「Ｓｉ－Ｏ結合のネットワークを形成させると共に相分離を行い、連続貫通流路と化学種を溶解できるシリコーン骨格」を形成させるには、相分離を制御するための界面活性剤（相分離制御剤）が必要であった。 According to the manufacturing method described in Patent Document 1, although a silicone monolith having excellent flexibility can be manufactured, "a network of Si—O bonds is formed and phase separation is performed, and continuous through channels and chemical species In order to form a "silicone skeleton capable of dissolving", a surfactant (phase separation control agent) was required to control phase separation.
　合成されたモノリス体から界面活性剤を除去するには、通常は多量の溶媒を用いて洗浄しなければならず、コスト、及び、環境負荷等の観点で改善の余地があった。 　In order to remove the surfactant from the synthesized monolith, it usually had to be washed with a large amount of solvent, and there was room for improvement in terms of cost and environmental impact.
　そこで、本発明は、ポリシロキサンから構成される骨格を有しながら、優れた柔軟性を有するポリシロキサン多孔体を、界面活性剤を用いなくても製造できる、ポリシロキサン多孔体の製造方法を提供することを課題とする。また、本発明は、ポリシロキサン多孔体、保温材、及び、保温容器を提供することも課題とする。 Therefore, the present invention provides a method for producing a polysiloxane porous body that can produce a polysiloxane porous body having a skeleton composed of polysiloxane and having excellent flexibility without using a surfactant. The task is to Another object of the present invention is to provide a polysiloxane porous body, a heat insulating material, and a heat insulating container.
　本発明者らは、上記課題を達成すべく鋭意検討した結果、以下の構成により上記課題を達成することができることを見出した。 As a result of intensive studies aimed at achieving the above problems, the inventors found that the above problems can be achieved with the following configuration.
［１］　テトラアルコキシシランと、メチルトリアルコキシシランと、ジメチルジアルコキシシランと、水とを含む組成物を調製し、ゲル化させてゲルを形成することと、上記ゲルを乾燥させてポリシロキサン多孔体を得ることと、を含み、上記組成物中における上記テトラアルコキシシランと、上記メチルトリアルコキシシランと、上記ジメチルジアルコキシシランの含有量の合計を１００モル％としたとき、上記テトラアルコキシシランの含有量が、１０．５～２０．０モル％であり、上記ジメチルジアルコキシシランの含有量が１１．０～４１．０モル％である、ポリシロキサン多孔体の製造方法。
［２］　上記組成物が、界面活性剤を含まない、［１］に記載のポリシロキサン多孔体の製造方法。
［３］　上記ジメチルジアルコキシシランの含有量が３８．０モル％以下である、［１］又は［２］に記載のポリシロキサン多孔体の製造方法。
［４］　上記メチルトリアルコキシシランの含有量が５０．０モル％以上であって、上記テトラアルコキシシランの含有量が１７．０モル％以上である、［３］に記載のポリシロキサン多孔体の製造方法。
［５］　上記メチルトリアルコキシシランの含有量が６７．０モル％以上である、［３］に記載のポリシロキサン多孔体の製造方法。
 ［６］　上記ポリシロキサン多孔体のかさ密度が０．３００ｇｃｍ－３以下である、［１］～［５］のいずれかに記載のポリシロキサン多孔体の製造方法。
 ［７］　２０℃における熱伝導率が０．０４００Ｗ／（ｍ・Ｋ）以下である、［１］～［６］のいずれかに記載のポリシロキサン多孔体の製造方法。
［８］　テトラアルコキシシランと、メチルトリアルコキシシランと、ジメチルジアルコキシシランと、水とを含む組成物を加水分解縮合させて得られるポリシロキサン多孔体であって、上記組成物中における上記テトラアルコキシシランと、上記メチルトリアルコキシシランと、上記ジメチルジアルコキシシランの含有量の合計を１００モル％としたとき、上記テトラアルコキシシランの含有量が、１０．５～２０．０モル％であり、上記ジメチルジアルコキシシランの含有量が１１．０～４１．０モル％である、ポリシロキサン多孔体。
［９］　上記組成物中における上記ジメチルジアルコキシシランの含有量が３８．０モル％以下である、［８］に記載のポリシロキサン多孔体。
［１０］　上記組成物中における、上記メチルトリアルコキシシランの含有量が５０．０モル％以上であって、上記テトラアルコキシシランの含有量が１７．０モル％以上である、［９］に記載のポリシロキサン多孔体。
［１１］　上記組成物中における、上記メチルトリアルコキシシランの含有量が６７．０モル％以上である、［９］に記載のポリシロキサン多孔体。
［１２］　かさ密度が０．３００ｇｃｍ－３以下である、［８］～［１１］のいずれかに記載のポリシロキサン多孔体。
 ［１３］　２０℃における熱伝導率が０．０４００Ｗ／（ｍ・Ｋ）以下である、［８］～［１２］のいずれかに記載のポリシロキサン多孔体。
［１４］　［８］～［１３］のいずれかに記載のポリシロキサン多孔体を含む保温材。
［１５］　［１４］に記載の保温材を備える保温容器。 [1] preparing a composition containing tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, and water, gelling to form a gel, and drying the gel to form polysiloxane pores; When the total content of the tetraalkoxysilane, the methyltrialkoxysilane, and the dimethyldialkoxysilane in the composition is 100 mol%, the content of the tetraalkoxysilane is A method for producing a polysiloxane porous body, wherein the content is 10.5 to 20.0 mol%, and the content of the dimethyldialkoxysilane is 11.0 to 41.0 mol%.
[2] The method for producing a polysiloxane porous material according to [1], wherein the composition does not contain a surfactant.
[3] The method for producing a polysiloxane porous body according to [1] or [2], wherein the content of the dimethyldialkoxysilane is 38.0 mol% or less.
[4] The polysiloxane porous material according to [3], wherein the content of the methyltrialkoxysilane is 50.0 mol% or more and the content of the tetraalkoxysilane is 17.0 mol% or more. Production method.
[5] The method for producing a polysiloxane porous body according to [3], wherein the content of the methyltrialkoxysilane is 67.0 mol % or more.
[6] The method for producing a polysiloxane porous body according to any one of [1] to [5], wherein the polysiloxane porous body has a bulk density of 0.300 gcm −3 or less.
[7] The method for producing a polysiloxane porous material according to any one of [1] to [6], which has a thermal conductivity of 0.0400 W/(m·K) or less at 20°C.
[8] A polysiloxane porous body obtained by hydrolytic condensation of a composition containing tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, and water, wherein the tetraalkoxy in the composition When the total content of the silane, the methyltrialkoxysilane, and the dimethyldialkoxysilane is 100 mol%, the content of the tetraalkoxysilane is 10.5 to 20.0 mol%. A polysiloxane porous body containing 11.0 to 41.0 mol % of dimethyldialkoxysilane.
[9] The polysiloxane porous body according to [8], wherein the content of the dimethyldialkoxysilane in the composition is 38.0 mol% or less.
[10] According to [9], the content of the methyltrialkoxysilane in the composition is 50.0 mol% or more, and the content of the tetraalkoxysilane is 17.0 mol% or more. polysiloxane porous body.
[11] The polysiloxane porous body according to [9], wherein the content of the methyltrialkoxysilane in the composition is 67.0 mol% or more.
[12] The polysiloxane porous body according to any one of [8] to [11], which has a bulk density of 0.300 gcm −3 or less.
[13] The polysiloxane porous body according to any one of [8] to [12], which has a thermal conductivity of 0.0400 W/(m·K) or less at 20°C.
[14] A heat insulating material containing the polysiloxane porous material according to any one of [8] to [13].
[15] A heat insulating container comprising the heat insulating material according to [14].
　本発明によれば、ポリシロキサンから構成される骨格を有しながら、優れた柔軟性を有するポリシロキサン多孔体を、界面活性剤を用いなくても製造できる、ポリシロキサン多孔体の製造方法が提供できる。また、本発明は、ポリシロキサン多孔体、保温材、及び、保温容器も提供できる。 INDUSTRIAL APPLICABILITY According to the present invention, there is provided a method for producing a polysiloxane porous body that can produce a polysiloxane porous body having a skeleton composed of polysiloxane and having excellent flexibility without using a surfactant. can. The present invention can also provide a polysiloxane porous body, a heat insulating material, and a heat insulating container.
組成物中における各ケイ素アルコキシドの成分の含有量を表す三角図である。Fig. 3 is a ternary diagram showing the content of each silicon alkoxide component in the composition. 本発明の一実施形態に係る保温容器１の全体構成を示す斜視図である。1 is a perspective view showing the overall configuration of a heat insulating container 1 according to one embodiment of the present invention; FIG. 保温容器の断面図である。It is a sectional view of a heat insulating container. 保温容器の分解断面図である。Fig. 3 is an exploded cross-sectional view of the heat insulating container; 保温材の斜視図である。It is a perspective view of a heat insulating material. 保温容器における保温材の装着方法を説明する図である。FIG. 4 is a diagram for explaining a method of attaching a heat insulating material to the heat insulating container; 保温容器の変形例である。It is a modification of the heat insulating container. 三角図に実施例の各組成物をプロットしたものである。1 is a ternary diagram plotted with each composition of the examples.
　以下、本発明について詳細に説明する。
　以下に記載する構成要件の説明は、本発明の代表的な実施形態に基づいてなされることがあるが、本発明はそのような実施形態に制限されるものではない。
　なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。 The present invention will be described in detail below.
Although the description of the constituent elements described below may be made based on representative embodiments of the present invention, the present invention is not limited to such embodiments.
In this specification, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
（用語の定義）
　本明細書において、「共連続構造」とは、部材（ポリシロキサン多孔体）の切断面を走査型電子顕微鏡で観察したとき、ポリシロキサンを主成分とする骨格相と空隙とがそれぞれ連続し、かつ、互いに三次元的に入り組んでいる状態を意味する。 (Definition of terms)
As used herein, the term “co-continuous structure” means that when a cut surface of a member (polysiloxane porous body) is observed with a scanning electron microscope, a skeleton phase containing polysiloxane as a main component and voids are continuous, Also, it means a state in which they are three-dimensionally intertwined with each other.
　また、本明細書において「マクロ孔」とは、ＩＵＰＡＣによる提唱に従い、孔径（細孔径）が５０ｎｍ以上の細孔を意味する。細孔の孔径、及び、平均孔径は、電子顕微鏡観察像の画像解析により求められる。 In addition, the term "macropores" as used herein means pores with a pore diameter (pore diameter) of 50 nm or more according to the proposal by IUPAC. The pore size and average pore size of the pores are determined by image analysis of electron microscopic images.
［ポリシロキサン多孔体の製造方法］
　本発明のポリシロキサン多孔体の製造方法（以下「本製造方法」ともいう。）は、テトラアルコキシシラン（ＴＥＡＳ）と、メチルトリアルコキシシラン（ＭＴＡＳ）と、ジメチルジアルコキシシラン（ＤＭＤＡＳ）と、水とを含む組成物を調製し、ゲル化させてゲルを形成することと、上記ゲルを乾燥させてポリシロキサン多孔体を得る、ポリシロキサン多孔体の製造方法であって、組成物中のＴＥＡＳ＋ＭＴＡＳ＋ＤＭＤＡＳ＝１００モル％としたとき、１０．５≦ＴＥＡＳ≦２０．０、かつ、１１．０≦ＤＭＤＡＳ≦４１．０が成り立つ、ポリシロキサン多孔体の製造方法である。なお、以下の説明では、ＴＥＡＳ、ＭＴＡＳ、及び、ＤＭＤＡＳをあわせて単に「ケイ素アルコキシド」ということがある。 [Manufacturing method of polysiloxane porous body]
The method for producing a polysiloxane porous material of the present invention (hereinafter also referred to as "the present production method") comprises tetraalkoxysilane (TEAS), methyltrialkoxysilane (MTAS), dimethyldialkoxysilane (DMDAS), and water. and gelling to form a gel, and drying the gel to obtain a polysiloxane porous body, wherein TEAS+MTAS+DMDAS in the composition= This method for producing a polysiloxane porous body satisfies 10.5≦TEAS≦20.0 and 11.0≦DMDAS≦41.0 when 100 mol %. In the following description, TEAS, MTAS and DMDAS may be collectively simply referred to as "silicon alkoxide".
　本発明者は、優れた柔軟性を有するシリコーン骨格モノリス体を、界面活性剤を用いなくても製造できる方法を検討してきた。
　シリコーン骨格モノリス体の合成は、いわゆるゾル－ゲル反応で進行する。従って、加水分解性基を有する多官能ケイ素アルコキシドを含む組成物を準備し、その組成物中でケイ素アルコキシドの加水分解生成物の重縮合体、すなわち、ゲルの骨格相であるポリシロキサンを順次増加させることで製造される。 The present inventor has investigated a method for producing a silicone skeleton monolith having excellent flexibility without using a surfactant.
Synthesis of a silicone skeleton monolith proceeds through a so-called sol-gel reaction. Therefore, a composition containing a polyfunctional silicon alkoxide having a hydrolyzable group is prepared, and the polycondensate of the hydrolysis product of the silicon alkoxide in the composition, that is, polysiloxane, which is the skeleton phase of the gel, is sequentially increased. It is manufactured by letting
　このとき、上記骨格相と未反応のケイ素アルコキシド等を含む溶液相との間で起こる相分離を粘弾性相分離となるよう調整することで骨格相、及び、溶液相がそれぞれ連続した３次元の網目構造を有すると共に互いに絡み合った共連続構造を形成させる。 At this time, by adjusting the phase separation that occurs between the skeleton phase and the solution phase containing unreacted silicon alkoxide and the like to be viscoelastic phase separation, the skeleton phase and the solution phase are each continuous three-dimensional. A co-continuous structure having a mesh structure and being entangled with each other is formed.
　この共連続構造は、ポリシロキサン多孔体に優れた柔軟性を与える要因の一つである。そのため、優れた柔軟性を有するシリコーン骨格モノリス体の製造には、相分離を制御するための界面活性剤（相分離制御剤）が不可欠だと考えられてきた。 This co-continuous structure is one of the factors that give the polysiloxane porous material excellent flexibility. Therefore, it has been thought that a surfactant (phase separation control agent) for controlling phase separation is essential for the production of a silicone skeleton monolith having excellent flexibility.
　本発明者は上記の技術常識にとらわれず、鋭意検討を続けた結果、モノマーとして、ＴＥＡＳ、ＭＴＡＳ、及び、ＤＭＤＡＳを併用し、更に、モノマーと水とを含む組成物中における各モノマーの含有量を所定の範囲とれば、相分離挙動を制御し、粘弾性相分離を起こさせ、優れた柔軟性を有するポリシロキサン多孔体を得られることを、膨大な組成を試した末に遂に発見し、本発明を完成させた。以下では、そのポリシロキサン多孔体の製造方法について詳述する。 The present inventors have made intensive studies without being bound by the above common technical knowledge. is within a predetermined range, the phase separation behavior can be controlled, viscoelastic phase separation can be caused, and a polysiloxane porous body having excellent flexibility can be obtained. I completed the present invention. The method for producing the polysiloxane porous body will be described in detail below.
（テトラアルコキシシラン：ＴＥＡＳ）
　まず、本製造方法に用いる各モノマー成分について説明する。
　本製造方法に用いるテトラアルコキシシランは、Ｒ１をアルキル基としたとき、式１：Ｓｉ－（ＯＲ１）４で表される化合物である（分子中に複数あるＲ１は同一でも異なってもよいが、同一であることが好ましい。）。 (Tetraalkoxysilane: TEAS)
First, each monomer component used in this production method will be described.
The tetraalkoxysilane used in this production method is a compound represented by the formula 1: Si—(OR 1 ) 4 where R 1 is an alkyl group (a plurality of R 1s in the molecule may be the same or different). but preferably identical).
　Ｒ１のアルキル基は、直鎖状、分岐鎖状、及び、環状のいずれであってもよいが、より優れた本発明の効果が得られる点で、直鎖状、又は、分岐鎖状のアルキル基が好ましい。
　Ｒ１の炭素数としては特に制限されないが、加水分解縮合により生ずるアルコールがより優れた親水性を有することから、１～１０個が好ましい。 The alkyl group for R 1 may be linear, branched, or cyclic. Alkyl groups are preferred.
Although the number of carbon atoms in R 1 is not particularly limited, it is preferably 1 to 10 because the alcohol produced by hydrolytic condensation has superior hydrophilicity.
　炭素数が１～１０個の直鎖状、又は、分岐鎖状のアルキル基としては、以下の基が挙げられる。炭素数が１個のメチル基；炭素数が２個のエチル基；炭素数が３個のプロピル基、イソプロピル基；炭素数が４個のブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｓｅｃ－ブチル基；炭素数が５個のペンチル基、１－メチルブチル基、２－メチルブチル基、３－メチルブチル基、１，１－ジメチルプロピル基、２，２－ジメチルプロピル基、１－エチルプロピル基；炭素数が６個のヘキシル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基、１，１－ジメチルブチル基、１，２－ジメチルブチル基、１，３－ジメチルブチル基、１，４－ジメチルブチル基、２，３－ジメチルブチル基、２，２－ジメチルブチル基、３，３－ジメチルブチル基、１－エチルブチル基、２－エチルブチル基、１－エチル－２－メチル－プロピル基、１，１，２－トリメチルプロピル基；炭素数が７個のヘプチル基、１－メチルヘキシル基、２－メチルヘキシル基、３－メチルヘキシル基、４－メチルヘキシル基、５－メチルヘキシル基、１，１－ジメチルペンチル基、２，２－ジメチルペンチル基、３，３－ジメチルペンチル基、４，４－ジメチルペンチル基、１，２－ジメチルペンチル基、１，３－ジメチルペンチル基、１，４－ジメチルペンチル基、２，３－ジメチルペンチル基、２，４－ジメチルペンチル基、３，４－ジメチルペンチル基、１－エチルペンチル基、２－エチルペンチル基、３－エチルペンチル基、１，２，２－トリメチルブチル基、１，１，２－トリメチルブチル基、１，３，３－トリメチルブチル基、１，１，３－トリメチルブチル基、２，２，３－トリメチルブチル基、２，３，３－トリメチルブチル基；炭素数が８個のオクチル基、１－メチルヘプチル基、２－メチルヘプチル基、３－メチルヘプチル基、４－メチルヘプチル基、５－メチルヘプチル基、６－メチルヘプチル基、１－エチルヘキシル基、２－エチルヘキシル基、３－エチルヘキシル基、４－エチルヘキシル基、１－プロピルペンチル基、２－プロピルペンチル基、１，１－ジメチルヘキシル基、２，２－ジメチルヘキシル基、３，３－ジメチルヘキシル基、４，４－ジメチルヘキシル基、５，５－ジメチルヘキシル基、３－エチル－３－メチルペンチル基、１，１－ジエチルブチル基、２，２－ジエチルブチル基、１，１，２，２－テトラメチルブチル基、１，１，３，３－テトラメチルブチル基、２，２，３，３－テトラメチルブチル基、１，１－ジメチル－２－エチルブチル基；炭素数が９個のノニル基、２－メチルオクチル基、３－メチルオクチル基、４－メチルオクチル基、２，２－ジメチルヘプチル基、２，３－ジメチルヘプチル基、２，４ジメチルヘプチル基、２，６ジメチルヘプチル基、３，３ジメチルヘプチル基、３，４ジメチルヘプチル基、３，５ジメチルヘプチル基、４，４ジメチルヘプチル基、３－エチルヘプチル基、４－エチルヘプチル基、２，２，３－トリメチルヘキシル基、２，２，４－トリメチルヘキシル基、２，２，５－トリメチルヘキシル基、２，３，３－トリメチルヘキシル基、２，３，４－トリメチルヘキシル基、２，３，５－トリメチルヘキシル基、２，４，４－トリメチルヘキシル基、３，３，４－トリメチルヘキシル基、２メチル－３－エチルヘキシル基、３－メチル－３－エチルヘキシル基、３－エチル－４－メチルヘキシル基、３－エチル－５－メチルヘキシル基、２，２，３，３－テトラメチルペンチル基、２，２，３，４－テトラメチルペンチル基、２，２，４，４－テトラメチルペンチル基、２，３，３，４－テトラメチルペンチル基、２，２－ジメチル－３－エチルペンチル基、２，３－ジメチル－３－エチルペンチル基、２，４－ジメチル－３－エチルペンチル基、３，３－ジエチルペンチル基；炭素数が１０個のデシル基、イソデシル基；等が挙げられる。 Examples of linear or branched alkyl groups having 1 to 10 carbon atoms include the following groups. methyl group with 1 carbon atom; ethyl group with 2 carbon atoms; propyl group with 3 carbon atoms, isopropyl group; butyl group with 4 carbon atoms, isobutyl group, tert-butyl group, sec-butyl Group; pentyl group having 5 carbon atoms, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group; carbon number is six hexyl groups, 1-methylpentyl groups, 2-methylpentyl groups, 3-methylpentyl groups, 4-methylpentyl groups, 1,1-dimethylbutyl groups, 1,2-dimethylbutyl groups, 1,3 -dimethylbutyl group, 1,4-dimethylbutyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-ethyl -2-methyl-propyl group, 1,1,2-trimethylpropyl group; heptyl group having 7 carbon atoms, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group , 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 3,3-dimethylpentyl group, 4,4-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3 -dimethylpentyl group, 1,4-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3 -ethylpentyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1,3,3-trimethylbutyl group, 1,1,3-trimethylbutyl group, 2,2,3 -trimethylbutyl group, 2,3,3-trimethylbutyl group; octyl group having 8 carbon atoms, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5- methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 3-ethyl-3-methylpentyl group, 1,1-diethylbutyl group, 2,2-diethylbutyl group, 1,1,2,2-tetramethylbutyl group, 1,1,3,3-tetramethylbutyl group group, 2,2,3,3-tetramethylbutyl group, 1,1-dimethyl-2-ethylbutyl group; nonyl group having 9 carbon atoms, 2-methyloctyl group, 3-methyloctyl group, 4- methyloctyl group, 2,2-dimethylheptyl group, 2,3-dimethylheptyl group, 2,4 dimethylheptyl group, 2,6 dimethylheptyl group, 3,3 dimethylheptyl group, 3,4 dimethylheptyl group, 3, 5-dimethylheptyl group, 4,4-dimethylheptyl group, 3-ethylheptyl group, 4-ethylheptyl group, 2,2,3-trimethylhexyl group, 2,2,4-trimethylhexyl group, 2,2,5- trimethylhexyl group, 2,3,3-trimethylhexyl group, 2,3,4-trimethylhexyl group, 2,3,5-trimethylhexyl group, 2,4,4-trimethylhexyl group, 3,3,4- trimethylhexyl group, 2methyl-3-ethylhexyl group, 3-methyl-3-ethylhexyl group, 3-ethyl-4-methylhexyl group, 3-ethyl-5-methylhexyl group, 2,2,3,3-tetra methylpentyl group, 2,2,3,4-tetramethylpentyl group, 2,2,4,4-tetramethylpentyl group, 2,3,3,4-tetramethylpentyl group, 2,2-dimethyl-3 -ethylpentyl group, 2,3-dimethyl-3-ethylpentyl group, 2,4-dimethyl-3-ethylpentyl group, 3,3-diethylpentyl group; decyl group having 10 carbon atoms, isodecyl group; is mentioned.
　また、環状のアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、及び、シクロヘキシル基等が挙げられる。また、環状のアルケニル基としては、シクロプロペニル基、シクロブテニル基、シクロペンテニル基、シクロペンタジエニル基、シクロヘキセニル基、シクロヘキサジエニル基、シクロヘプテニル基、シクロヘプタジエニル基、シクロオクテニル基、及び、シクロオクタジエニル基等が挙げられる。また、環状のアルキニル基としては、シクロアルケニル基；シクロオクチニル基、シクロノニニル基、シクロデシニル基、及び、シクロデカジイニル基等が挙げられる。 In addition, the cyclic alkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. As the cyclic alkenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, a cyclohexadienyl group, a cycloheptenyl group, a cycloheptadienyl group, a cyclooctenyl group, and a cyclo octadienyl group and the like. Moreover, a cyclic alkynyl group includes a cycloalkenyl group; a cyclooctynyl group, a cyclononynyl group, a cyclodecynyl group, a cyclodecadiynyl group, and the like.
　ＴＥＡＳとしては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシラン、テトラブトキシシラン、及び、テトラキス（２－エチルヘキシルオキシ）シラン等が挙げられ、反応の制御のしやすさ、コストの点からはテトラメトキシシラン（ＴＭＯＳ）が好ましい。 Examples of TEAS include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, and the like. From the viewpoint of cost, tetramethoxysilane (TMOS) is preferred.
（メチルトリアルコキシシラン：ＭＴＡＳ）
　本製造方法に用いるメチルトリアルコキシシランは、Ｒ２をアルキル基としたとき、式２：ＣＨ３－Ｓｉ－（ＯＲ２）３で表される化合物である（分子中に複数あるＲ２は同一でも異なってもよいが、同一であることが好ましい。）。 (Methyltrialkoxysilane: MTAS)
The methyltrialkoxysilane used in this production method is a compound represented by the formula 2: CH 3 —Si—(OR 2 ) 3 where R 2 is an alkyl group (a plurality of R 2 in the molecule are the same may be different, but are preferably the same).
　なお、Ｒ２のアルキル基は、Ｒ１のアルキル基と同義であり、好適形態も同様である。 The alkyl group for R2 has the same meaning as the alkyl group for R1 , and the preferred forms are also the same.
　ＭＴＡＳとしては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリイソプロポキシシラン、及び、メチルトリブトキシシラン等が挙げられ、メチルトリメトキシシラン（ＭＴＭＳ）が好ましい。 Examples of MTAS include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, and methyltributoxysilane, and methyltrimethoxysilane (MTMS) is preferred.
（ジメチルジアルコキシシラン：ＤＭＤＡＳ）
　本製造方法に用いるジメチルジアルコキシシランは、Ｒ３をアルキル基としたとき、式３：（ＣＨ３）２－Ｓｉ－（ＯＲ３）２で表される化合物である（分子中に複数あるＲ３同一でも異なってもよいが、同一であることが好ましい。）。 (dimethyldialkoxysilane: DMDAS)
The dimethyldialkoxysilane used in this production method is a compound represented by the formula 3: (CH 3 ) 2 —Si—(OR 3 ) 2 where R 3 is an alkyl group (a plurality of R 3 may be the same or different, but are preferably the same).
　なお、Ｒ３のアルキル基は、Ｒ１のアルキル基と同義であり、好適形態も同様である。 The alkyl group for R3 has the same definition as the alkyl group for R1 , and the preferred forms are also the same.
　ＤＭＤＡＳとしては、例えば、ジメチルジメトキシシラン、及び、ジエトキシジメチルシラン等が挙げられ、ジメチルジメトキシシラン（ＤＭＤＭＳ）が好ましい。 Examples of DMDAS include dimethyldimethoxysilane, diethoxydimethylsilane, and the like, with dimethyldimethoxysilane (DMDMS) being preferred.
　次に、上記各モノマーを用いる本製造方法の製造工程について説明する。
　本製造方法は、ＴＥＡＳ、ＭＴＡＳ、及び、ＤＭＤＡＳ、並びに、水を含む組成物を調製し、ゲル化させてゲルを形成することと、得られたゲルを乾燥させることを含む。 Next, the production steps of this production method using each of the above monomers will be described.
The manufacturing method includes preparing a composition comprising TEAS, MTAS, DMDAS, and water, gelling to form a gel, and drying the resulting gel.
　上記組成物中における、ＴＥＡＳの含有量は、ＴＥＡＳ、ＭＴＡＳ、及び、ＤＭＤＡＳの合計を１００モル％としたとき、１０．５～２０．０モル％である（１０．５モル％≦ＴＥＡＳ≦２０．０モル％）。
　ＴＥＡＳが１０．５モル％未満であったり、２０．０モル％を超えたりすると、界面活性剤を用いない系では、優れた柔軟性を有するポリシロキサン多孔体が得られない。 The content of TEAS in the composition is 10.5 to 20.0 mol% when the total of TEAS, MTAS and DMDAS is 100 mol% (10.5 mol% ≤ TEAS ≤ 20 mol% .0 mol %).
If TEAS is less than 10.5 mol % or more than 20.0 mol %, a polysiloxane porous body having excellent flexibility cannot be obtained in a system that does not use a surfactant.
　また、ＤＭＤＡＳの含有量は、ＴＥＡＳ、ＭＴＡＳ、及び、ＤＭＤＡＳの合計を１００モル％としたとき、１１．０～４１．０モル％である（１１．０モル％≦ＤＭＤＡＳ≦４１．０モル％）。
　ＤＭＤＡＳが１１．０モル％未満であったり、４１．０モル％を超えたりすると、界面活性剤を用いない系では、優れた柔軟性を有するポリシロキサン多孔体が得られない。 The content of DMDAS is 11.0 to 41.0 mol% when the total of TEAS, MTAS and DMDAS is 100 mol% (11.0 mol% ≤ DMDAS ≤ 41.0 mol% ).
If DMDAS is less than 11.0 mol % or more than 41.0 mol %, a polysiloxane porous body having excellent flexibility cannot be obtained in a system that does not use a surfactant.
　また、ＭＴＡＳの含有量は、ＴＥＡＳ、ＭＴＡＳ、及び、ＤＭＤＡＳの合計を１００モル％としたとき、３９．０～７８．５モル％である（３９．０モル％≦ＭＴＡＳ≦７８．５モル％）。
　以上をまとめると、本組成物中におけるケイ素アルコキシドの含有量は、
１０．５モル％≦ＴＥＡＳ　≦２０．０モル％、
１１．０モル％≦ＤＭＤＡＳ≦４１．０モル％、かつ、
３９．０モル％≦ＭＴＡＳ　≦７８．５モル％、
である。
　図１は、組成物中における上記各ケイ素アルコキシドの成分の含有量を表す三角図である。このうち上記数値範囲を満たすのは、図１中の網掛けの部分である。 The content of MTAS is 39.0 to 78.5 mol% when the total of TEAS, MTAS and DMDAS is 100 mol% (39.0 mol% ≤ MTAS ≤ 78.5 mol% ).
To summarize the above, the content of silicon alkoxide in the present composition is
10.5 mol% ≤ TEAS ≤ 20.0 mol%,
11.0 mol% ≤ DMDAS ≤ 41.0 mol%, and
39.0 mol%≤MTAS≤78.5 mol%,
is.
FIG. 1 is a ternary diagram showing the content of each silicon alkoxide component in the composition. Of these, the shaded portion in FIG. 1 satisfies the above numerical range.
　なかでも、得られるポリシロキサン多孔体がより優れた断熱性（より低い熱伝導率）を有する観点からは、組成物中におけるＤＭＤＡＳの含有量は、３８．０モル％以下が好ましい。
　すなわち、より優れた断熱性を有するポリシロキサン多孔体が得られる観点では、組成物中におけるケイ素アルコキシドの含有量が、それぞれ以下の範囲であることが好ましい。
１０．５モル％≦ＴＥＡＳ　≦２０．０モル％、
１１．０モル％≦ＤＭＤＡＳ≦３８．０モル％、かつ、
３９．０モル％≦ＭＴＡＳ　≦７８．５モル％ Above all, the content of DMDAS in the composition is preferably 38.0 mol % or less from the viewpoint that the resulting polysiloxane porous body has superior heat insulating properties (lower thermal conductivity).
That is, from the viewpoint of obtaining a polysiloxane porous body having superior heat insulating properties, the silicon alkoxide content in the composition is preferably within the following ranges.
10.5 mol% ≤ TEAS ≤ 20.0 mol%,
11.0 mol% ≤ DMDAS ≤ 38.0 mol%, and
39.0 mol% ≤ MTAS ≤ 78.5 mol%
　また、更に優れた断熱性を有するポリシロキサン多孔体が得られる観点からは、ＤＭＤＡＳの含有量が３８．０モル％以下であって、ＭＴＡＳの含有量が５０．０モル％以下であって、かつ、ＴＥＡＳの含有量が１７．０モル％以上であることがより好ましい。すなわち、更に優れた断熱性を有するポリシロキサン多孔体が得られる観点では、組成物中におけるケイ素アルコキシドの含有量が、それぞれ以下の範囲であることがより好ましい。
１７．０モル％≦ＴＥＡＳ　≦２０．０モル％、
１１．０モル％≦ＤＭＤＡＳ≦３８．０モル％、かつ、
３９．０モル％≦ＭＴＡＳ　≦５０モル％
　なお、この場合、ＤＭＤＡＳは、３０．０モル％以上であることが好ましい。
　すなわち、３０．０モル％≦ＤＭＤＡＳ≦３８．０モル％であることが好ましい。 Further, from the viewpoint of obtaining a polysiloxane porous body having even better heat insulating properties, the content of DMDAS is 38.0 mol% or less and the content of MTAS is 50.0 mol% or less, Moreover, it is more preferable that the content of TEAS is 17.0 mol % or more. That is, from the viewpoint of obtaining a polysiloxane porous body having even better heat insulating properties, it is more preferable that the content of the silicon alkoxide in the composition is within the following ranges.
17.0 mol% ≤ TEAS ≤ 20.0 mol%,
11.0 mol% ≤ DMDAS ≤ 38.0 mol%, and
39.0 mol% ≤ MTAS ≤ 50 mol%
In this case, DMDAS is preferably 30.0 mol % or more.
That is, it is preferable that 30.0 mol %≦DMDAS≦38.0 mol %.
　また、他の形態として、ＤＭＤＡＳの含有量が３８．０モル％以下であって、かつ、ＭＴＡＳの含有量が６７．０モル％以上であると、更に優れた断熱性を有するポリシロキサン多孔体が得られる。
１０．５モル％≦ＴＥＡＳ　≦２０．０モル％、
１１．０モル％≦ＤＭＤＡＳ≦３８．０モル％、かつ、
６７．０モル％≦ＭＴＡＳ　≦７８．５モル％ Further, as another embodiment, a polysiloxane porous body having a further excellent heat insulating property when the content of DMDAS is 38.0 mol% or less and the content of MTAS is 67.0 mol% or more is obtained.
10.5 mol% ≤ TEAS ≤ 20.0 mol%,
11.0 mol% ≤ DMDAS ≤ 38.0 mol%, and
67.0 mol% ≤ MTAS ≤ 78.5 mol%
　組成物は、水を含有する。組成物中における水の含有量としては特に制限されないが、０．１～９０質量％が好ましい。組成物は、すでに説明した各成分を混合することによって調製できる。
　なかでも、得られるポリシロキサン多孔体が、より優れた断熱性（より小さな熱伝導率）を有する観点で、溶媒の含有量は、組成物の全質量を１００質量％としたとき、５０質量％以上が好ましく、５５質量％以上がより好ましく、５７質量％以上が更に好ましい。 The composition contains water. Although the content of water in the composition is not particularly limited, it is preferably 0.1 to 90% by mass. The composition can be prepared by mixing the ingredients previously described.
Among them, the content of the solvent is 50% by mass when the total mass of the composition is 100% by mass, from the viewpoint that the obtained polysiloxane porous body has better heat insulation (lower thermal conductivity). 55% by mass or more is more preferable, and 57% by mass or more is even more preferable.
　組成物は、界面活性剤を含まないことが好ましい。組成物が界面活性剤を含有しないとは、ＴＥＡＳ、ＭＴＡＳ、及び、ＤＭＤＡＳのケイ素（合計）の１モルに対して、界面活性剤の含有量が、０．００１モル未満であることを意味し、０．０００１モル以下が好ましく、０．００００１モル以下がより好ましい。 The composition preferably does not contain surfactants. By the composition being surfactant-free, it is meant that the surfactant content is less than 0.001 mol per 1 mol of silicon (total) of TEAS, MTAS and DMDAS. , is preferably 0.0001 mol or less, more preferably 0.00001 mol or less.
　界面活性剤は、カチオン性、アニオン性、両性、及び、非イオン（ノニオン）性が挙げられる。 Surfactants include cationic, anionic, amphoteric, and nonionic.
　アニオン性界面活性剤としては、例えば、ヘキシルベンゼンスルホン酸、オクチルベンゼンスルホン酸、デシルベンゼンスルホン酸、ドデシルベンゼンスルホン酸、セチルベンゼンスルホン酸、ミリスチルベンゼンスルホン酸、ラウリル硫酸、ポリオキシエチレンラウリル硫酸、ドデセンスルホン酸、テトラデセンスルホン酸、ヘキサデセンスルホン酸、ヒドロキシドデカンスルホン酸、ヒドロキシテトラデカンスルホン酸、ヒドロキシヘキサデカンスルホン酸、並びに、これらのナトリウム塩、カリウム塩、アンモニウム塩、及び、トリエタノールアミン塩等が挙げられる。 Examples of anionic surfactants include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid, lauryl sulfate, polyoxyethylene lauryl sulfate, de Decenesulfonic acid, tetradecenesulfonic acid, hexadecenesulfonic acid, hydroxydodecanesulfonic acid, hydroxytetradecanesulfonic acid, hydroxyhexadecanesulfonic acid, and their sodium salts, potassium salts, ammonium salts, and triethanolamine salts. be done.
　カチオン性界面活性剤としては、例えば、水酸化オクチルトリメチルアンモニウム、水酸化ラウリルトリメチルアンモニウム、水酸化ステアリルトリメチルアンモニウム、水酸化ジオクチルジメチルアンモニウム、水酸化ジステアリルジメチルアンモニウム、塩化ラウリルトリメチルアンモニウム、塩化ステアリルトリメチルアンモニウム、塩化セチルトリメチルアンモニウム、塩化ジココイルジメチルアンモニウム、塩化ジステアリルジメチルアンモニウム、塩化ベンザルコニウム、及び、塩化ステアリルジメチルベンジルアンモニウム等が挙げられる。 Examples of cationic surfactants include octyltrimethylammonium hydroxide, lauryltrimethylammonium hydroxide, stearyltrimethylammonium hydroxide, dioctyldimethylammonium hydroxide, distearyldimethylammonium hydroxide, lauryltrimethylammonium chloride, and stearyltrimethylammonium chloride. , cetyltrimethylammonium chloride, dicocoyldimethylammonium chloride, distearyldimethylammonium chloride, benzalkonium chloride, and stearyldimethylbenzylammonium chloride.
　ノニオン性界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンソルビトール脂肪酸エステル、ポリエチレングリコール、ポリプロピレングリコール、及び、ジエチレングリコール等が挙げられる。 Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, and polyoxyethylene sorbitol fatty acid ester. , polyethylene glycol, polypropylene glycol, and diethylene glycol.
　両性界面活性剤としては、例えば、アミノ酸型、及び、ベタイン酸型界面活性剤等が挙げられる。 Amphoteric surfactants include, for example, amino acid-type and betaic acid-type surfactants.
　組成物は、本発明の効果を奏する範囲内において、その他の成分を含有していてもよい。その他の成分としては、例えば、酸、及び、塩基等が挙げられる。 The composition may contain other ingredients within the scope of the effects of the present invention. Other components include, for example, acids and bases.
（酸）
　組成物は酸を含むことが好ましい。酸は、アルコキシシランを加水分解させ、硬化反応を触媒する。系中においてアルコキシシランが加水分解し、加水分解生成物が生じると、重縮合反応が順をおって次々と起こる。
　酸による加水分解は、Ｈ３Ｏ＋によって求電子的に進行する。すなわち、Ｈ３Ｏ＋はアルコキシ基の酸素原子を攻撃し、－Ｓｉ－ＯＨとアルコールとが生成する。この反応には立体障害の影響がなく、加水分解、重縮合が逐次進み、直鎖状のポリシロキサンが合成されやすい特徴がある。 (acid)
Preferably the composition contains an acid. The acid hydrolyzes the alkoxysilane and catalyzes the curing reaction. When alkoxysilane is hydrolyzed in the system to produce hydrolysis products, polycondensation reactions occur one after another in order.
Acid hydrolysis proceeds electrophilically with H 3 O + . That is, H 3 O + attacks the oxygen atom of the alkoxy group to generate -Si-OH and alcohol. This reaction has no effect of steric hindrance, hydrolysis and polycondensation proceed successively, and linear polysiloxane is easily synthesized.
　酸は、無機酸であっても有機酸であってもよく、無機酸としては、塩酸、及び、硫酸等が使用できる。また、有機酸としては、ギ酸、酢酸、プロピオン酸、シュウ酸、及び、クエン酸等が使用でき、加水分解反応の制御がより容易である点で、酢酸が好ましい。 The acid may be an inorganic acid or an organic acid. As the inorganic acid, hydrochloric acid, sulfuric acid, etc. can be used. As the organic acid, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, and the like can be used, and acetic acid is preferable because the hydrolysis reaction is easier to control.
　組成物中における酸の含有量としては特に制限されないが、ポリシロキサン多孔体がより優れた形状安定性と、より優れた柔軟性を有する点で、組成物中における水の含有量の１Ｌに対して１～１００ｍｍｏｌであることが好ましく、５～１０ｍｍｏｌがより好ましい。 The content of the acid in the composition is not particularly limited, but since the polysiloxane porous body has better shape stability and flexibility, the content of water in the composition is 1 L. is preferably 1 to 100 mmol, more preferably 5 to 10 mmol.
（塩基）
　組成物は塩基を含むことが好ましい。塩基は、アルコキシシランを加水分解させ、硬化反応を触媒する。塩基による加水分解ではＯＨ－による求核的に進行する。すなわち、ＯＨ－はケイ素原子を直接攻撃し、ＲＯ－を生成させる（Ｒは有機基である。）。
　この反応は立体障害等の影響により当初は進みにくいものの、一旦進行すると立体障害が軽減されて反応が急速に進行しやすい。その結果、重縮合に寄与するヒドロキシ基が増えるために、分枝状のポリシロキサンが合成されやすい。 (base)
Preferably, the composition contains a base. The base hydrolyzes the alkoxysilane and catalyzes the curing reaction. Hydrolysis with a base proceeds nucleophilically with OH- . That is, OH- directly attacks a silicon atom to generate RO- ( R is an organic group).
Although this reaction is initially difficult to proceed due to the effects of steric hindrance and the like, once it proceeds, the steric hindrance is alleviated and the reaction tends to proceed rapidly. As a result, the number of hydroxy groups that contribute to polycondensation increases, so branched polysiloxanes are easily synthesized.
　塩基としては特に制限されないが、水酸化カリウム、水酸化ナトリウム、及び、水酸化リチウム等のアルカリ金属水酸化物；水酸化カルシウム、水酸化ストロンチウム、及び、水酸化バリウム等のアルカリ土類金属水酸化物；炭酸カリウム、及び、炭酸ナトリウム等のアルカリ金属炭酸塩；アンモニア；モノメチルアミン、ジメチルアミン、トリエチルアミン、モノエチルアミン、ジエチルアミン、エチレンジアミン、モノエタノールアミン、ジエタノールアミン、及び、トリエタノールアミン等のアミン類等が挙げられる。 The base is not particularly limited, but alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide, and barium hydroxide. substances; alkali metal carbonates such as potassium carbonate and sodium carbonate; ammonia; amines such as monomethylamine, dimethylamine, triethylamine, monoethylamine, diethylamine, ethylenediamine, monoethanolamine, diethanolamine, and triethanolamine mentioned.
　また、分解反応により塩基性物質を生じさせる物質でもよく、このような物質としては、例えば、尿素、及び、ヘキサミン等が挙げられるが、これらのうちでは、水への溶解性や揮発性が高く除去が容易という点から、尿素が好ましい。 Substances that produce basic substances by decomposition reaction may also be used, and examples of such substances include urea and hexamine. Urea is preferred because it is easy to remove.
　組成物中における塩基の含有量としては特に制限されないが、ポリシロキサン多孔体がより優れた形状安定性と、より優れた柔軟性を有する点で、１ｍＭ～１５Ｍが好ましい。 Although the content of the base in the composition is not particularly limited, it is preferably from 1 mM to 15M in that the polysiloxane porous body has superior shape stability and flexibility.
　ポリシロキサン多孔体は、すでに説明した各成分を混合して得られた組成物を用いて、ゾル－ゲル法によるケイ素アルコキシドの加水分解と、その加水分解により得られるケイ素アルコキシドの加水分解生成物の重縮合と、重縮合により得られる重縮合体（ポリシロキサン）と未反応のケイ素アルコキシドや加水分解生成物を含む溶液系との相分離を並行することによって、骨格相と溶液相とから構成されるゲルを形成する工程（ゲル化工程）を含む。 The polysiloxane porous material is obtained by hydrolyzing silicon alkoxide by a sol-gel method using a composition obtained by mixing the components already described, and hydrolyzing the silicon alkoxide obtained by the hydrolysis. Polycondensation and phase separation of the polycondensate (polysiloxane) obtained by polycondensation and the solution system containing unreacted silicon alkoxide and hydrolysis products are performed in parallel to form a skeleton phase and a solution phase. including a step of forming a gel (gelation step).
　ゲル化工程において形成されるゲルの骨格相は、上記ケイ素アルコキシドの加水分解生成物の重縮合体に富んでいる。溶液相は上記組成物の溶媒に富んでおり、溶液相における上記重縮合体の含有量は骨格相における含有量に比べて相対的に少ない。
　相分離は、ケイ素アルコキシドの加水分解、及び、加水分解生成物の重縮合と同時に進行する相分離であり、典型的には粘弾性相分離である。このような相分離過程を経て生じた骨格相および溶液相は、それぞれ連続した３次元の網目構造を有すると共に互いに絡み合っている。 The skeleton phase of the gel formed in the gelling process is rich in polycondensates of the hydrolysis products of the silicon alkoxides. The solution phase is rich in the solvent of the composition and the content of the polycondensate in the solution phase is relatively low compared to the content in the skeleton phase.
Phase separation is phase separation that proceeds simultaneously with hydrolysis of silicon alkoxide and polycondensation of hydrolysis products, typically viscoelastic phase separation. The skeletal phase and solution phase generated through such a phase separation process each have a continuous three-dimensional network structure and are entangled with each other.
　ゲル化工程において形成するゲルは骨格相および溶液相の共連続構造を有する。また、骨格相を構成する上記重合体は、ゾル－ゲル反応による上記ケイ素アルコキシドの加水分解生成物の重縮合により形成されたシロキサン結合（－Ｓｉ－Ｏ－Ｓｉ－）のネットワークを有するポリシロキサンである。すなわち、ゲル化工程において形成するゲルは、ポリシロキサンゲルである。 The gel formed in the gelation process has a co-continuous structure of the skeleton phase and the solution phase. Further, the polymer constituting the skeleton phase is a polysiloxane having a network of siloxane bonds (--Si--O--Si--) formed by polycondensation of the hydrolysis product of the silicon alkoxide by a sol-gel reaction. be. That is, the gel formed in the gelation step is polysiloxane gel.
　ゲル化工程は、各成分を混合し、組成物を調製することで進行する。このとき組成物を加熱してもよい。加熱条件は特に制限されないが、一般に４０～１００℃が好ましく、加熱時間は２～４８時間が好ましい。 The gelation process proceeds by mixing each component and preparing a composition. At this time, the composition may be heated. Although the heating conditions are not particularly limited, 40 to 100° C. is generally preferred, and the heating time is preferably 2 to 48 hours.
　ゲル化工程により得られるゲルは、ポリシロキサンの湿潤ゲルである。乾燥工程は、この湿潤ゲルを乾燥させてポリシロキサン多孔体を得る工程である。乾燥の方法としては特に制限されないが、室温～１２０℃で１～２４時間保持する方法等が挙げられる。 The gel obtained by the gelation process is a wet gel of polysiloxane. The drying step is a step of drying the wet gel to obtain a polysiloxane porous body. The drying method is not particularly limited, but includes a method of holding at room temperature to 120° C. for 1 to 24 hours.
　加水分解性基を分子内に有するケイ素アルコキシドは、ゾル－ゲル反応による加水分解生成物の重縮合を経て、シロキサン結合のネットワークを形成する。本組成物は、２、３、及び、４官能のアルコキシシランを併用しているため、３、４官能のアルコキシシランか生ずる剛直なネットワークと、２官能のアルコキシシランから生ずる自由度が高い平面的で柔軟な結合が生じることになる。
　これにより、得られるポリシロキサン多孔体は、乾燥後においても、ポリシロキサンから構成される骨格を有しながら柔軟性を示す。 A silicon alkoxide having a hydrolyzable group in its molecule forms a network of siloxane bonds through polycondensation of hydrolysis products by a sol-gel reaction. Since the present composition uses di-, tri-, and tetra-functional alkoxysilanes in combination, a rigid network generated by tri- and tetra-functional alkoxysilanes and a planar network with a high degree of freedom generated by di-functional alkoxysilanes will result in a flexible connection.
As a result, the obtained polysiloxane porous material exhibits flexibility even after drying while having a skeleton composed of polysiloxane.
　本製造方法は本発明の効果を損なわない範囲内で上記以外の他の工程を有していてもよい。他の工程としては例えば、ポリシロキサン多孔体を加熱して脱水する工程が挙げられる。
　この時の加熱の温度としては特に制限されないが、２００℃を超えることが好ましい。ポリシロキサン多孔体中にシラノール（Ｓｉ－ＯＨ）が残留する場合、加熱により脱水することができる。なお、ポリシロキサン多孔体は優れた耐熱性を有しており、この工程により柔軟性が損なわれることはない。 The present production method may have other steps than those described above as long as the effects of the present invention are not impaired. Other steps include, for example, a step of heating and dehydrating the polysiloxane porous body.
Although the heating temperature at this time is not particularly limited, it is preferably higher than 200°C. If silanol (Si—OH) remains in the polysiloxane porous material, it can be dehydrated by heating. Since the polysiloxane porous material has excellent heat resistance, this step does not impair its flexibility.
（ポリシロキサン多孔体）
　上記方法により調製されるポリシロキサン多孔体は、ポリシロキサンから構成された骨格と、マクロ孔との共連続構造を有する。当該骨格を構成するポリシロキサンは、ＴＥＡＳ、ＭＴＡＳ、及び、ＤＭＤＡＳを含む組成物において、これらケイ素アルコキシドの加水分解、加水分解生成物の重縮合により形成されたポリシロキサンである。すなわち、水溶液中において所定のケイ素アルコキシドの重縮合反応に伴う粘弾性相分離により骨格形成されるシリコーン組成のモノリス型マクロ多孔性部材である。 (Polysiloxane porous body)
The polysiloxane porous material prepared by the above method has a co-continuous structure of a skeleton composed of polysiloxane and macropores. The polysiloxane constituting the skeleton is polysiloxane formed by hydrolysis of these silicon alkoxides and polycondensation of the hydrolysis products in the composition containing TEAS, MTAS and DMDAS. In other words, it is a monolithic macroporous member of a silicone composition whose skeleton is formed by viscoelastic phase separation that accompanies the polycondensation reaction of a given silicon alkoxide in an aqueous solution.
　柔軟性の程度は、例えば、ヤング率にして１００ｋＰａ以下である。このような高い柔軟性と、マクロ孔の存在による光の散乱のため無着色の状態で白色であることから、上記ポリシロキサン多孔体は、本発明者によって「マシュマロゲル」と名付けられた。 The degree of flexibility is, for example, 100 kPa or less in terms of Young's modulus. Due to such high flexibility and light scattering due to the presence of macropores, the polysiloxane porous material was named "marshmallow gel" by the present inventors because it is white in an uncolored state.
　上記ポリシロキサン多孔体は相分離過程を併用するゾル－ゲル反応を経て、骨格との共連続構造を有するマクロ孔が形成されるため、均一な孔径のマクロ孔を有する。このような構造は、発泡剤による発泡過程を経て得た多孔体の構造（このような多孔体では、発泡による独立した空孔が多数形成される）とは全く異なる。 The above polysiloxane porous material has macropores with a uniform pore size because macropores having a co-continuous structure with the skeleton are formed through a sol-gel reaction combined with a phase separation process. Such a structure is completely different from the structure of a porous body obtained through a foaming process using a foaming agent (in such a porous body, a large number of independent pores are formed by foaming).
　骨格の平均径は、例えば５００ｎｍ以上が好ましく、１０μｍ未満が好ましい。マクロ孔の平均孔径は、例えば５００ｎｍ～２００μｍである。
　ポリシロキサン多孔体が有する細孔の平均細孔径は、１μｍ以上が好ましく、１００μｍ未満が好ましい。なお、ポリシロキサン多孔体の骨格径、及び、平均細孔径は、電子顕微鏡観察像の画像解析により求められる。 The average diameter of the skeleton is, for example, preferably 500 nm or more and preferably less than 10 μm. The average pore size of macropores is, for example, 500 nm to 200 μm.
The average pore diameter of the pores of the polysiloxane porous body is preferably 1 μm or more, and preferably less than 100 μm. The skeleton diameter and average pore diameter of the polysiloxane porous material can be determined by image analysis of electron microscope observation images.
　上記ポリシロキサン多孔体の空孔率は、レーザー共焦点顕微鏡による測定値にして、例えば７５～９８％が好ましい。 The porosity of the polysiloxane porous material is preferably, for example, 75 to 98% as measured by a laser confocal microscope.
　上記ポリシロキサン多孔体は、骨格がポリシロキサンから構成されることに由来して、幅広い温度領域において安定である。例えば、液体窒素温度（－１９６℃）から、ポリシロキサンが分解される温度（およそ３２０℃）に至るまで、その柔軟性を保つことができる。 The above-mentioned polysiloxane porous body is stable in a wide temperature range because its skeleton is composed of polysiloxane. For example, it can retain its flexibility from liquid nitrogen temperature (−196° C.) to the temperature at which polysiloxane decomposes (approximately 320° C.).
　また、本ポリシロキサン多孔体は、優れた耐熱性と、優れた断熱性とを併せ持ち、熱伝導率としては特に制限されないが、２０℃（大気圧、空気中）の熱伝導率が、０．０４００Ｗ／（ｍ・Ｋ）以下が好ましく、０．０３５０Ｗ／（ｍ・Ｋ）以下がより好ましく、０．０３３０Ｗ／（ｍ・Ｋ）以下が更に好ましい。下限は特に制限されないが、一般に、０．０１２０Ｗ／（ｍ・Ｋ）以上が好ましい。
　なお、上記熱伝導率は、後述する実施例に記載の方法により測定される。 In addition, the present polysiloxane porous material has both excellent heat resistance and excellent heat insulating properties, and although there are no particular restrictions on the thermal conductivity, the thermal conductivity at 20° C. (atmospheric pressure, in air) is 0.5. 0400 W/(m·K) or less is preferable, 0.0350 W/(m·K) or less is more preferable, and 0.0330 W/(m·K) or less is even more preferable. The lower limit is not particularly limited, but generally 0.0120 W/(m·K) or more is preferable.
The thermal conductivity is measured by the method described in Examples below.
　また、本ポリシロキサン多孔体のかさ密度は特に制限されないが、０．３００ｇｃｍ－３（ｇ／ｃｍ３）以下が好ましく、０．２００ｇｃｍ－３以下がより好ましく、０．１１０ｇｃｍ－３以下が更に好ましい。下限は特に制限されないが、一般に、０．０１０ｇｃｍ－３以上が好ましい。 The bulk density of the present polysiloxane porous material is not particularly limited, but is preferably 0.300 gcm -3 (g/cm 3 ) or less, more preferably 0.200 gcm -3 or less, and even more preferably 0.110 gcm -3 or less. . Although the lower limit is not particularly limited, 0.010 gcm −3 or more is generally preferred.
　また、本ポリシロキサン多孔体は、優れた耐屈曲性を有している。５ｍｍの厚みのポリシロキサン多孔体を調製し、直径１０ｍｍの円柱（棒）に巻き付けた際、クラックが生じないことが好ましい。 In addition, the present polysiloxane porous body has excellent bending resistance. When a polysiloxane porous body having a thickness of 5 mm is prepared and wound around a cylinder (rod) having a diameter of 10 mm, it is preferable that no cracks occur.
　また、本ポリシロキサン多孔体は優れた柔軟性を有しており、平板状のポリシロキサン多孔体を調製し、全高に対する８０％（元の２０％の大きさになるように）の一軸圧縮を行い、除荷後に残る圧縮永久ひずみが１０％以下であることが好ましく、８％以下であることがより好ましく、５％以下であることが更に好ましい。 In addition, the present polysiloxane porous body has excellent flexibility, and a flat polysiloxane porous body is prepared and uniaxially compressed to 80% of the total height (to 20% of the original size). The compression set remaining after unloading is preferably 10% or less, more preferably 8% or less, and even more preferably 5% or less.
　また、本ポリシロキサン多孔体は外部からの圧縮による変形をうけた際も熱伝導率の変化がより小さいことが好ましい。熱伝導率の変化率としては特に制限されないが、一軸圧縮による圧縮率が６０％（全高が１００％から４０％になる）のとき、無圧縮（圧縮率０％）の際の熱伝導率と比較した熱伝導率の変化率が、１０．０％以下であることが好ましく、６．０％以下であることがより好ましい。
　なお、熱伝導率の変化率は、圧縮前の熱伝導率に対する、圧縮後の熱伝導率と圧縮前の熱伝導率の差の絶対値の比を百分率で表したものである。すなわち、式：熱伝導率の変化率＝｜圧縮後の熱伝導率－圧縮前の熱伝導率｜／圧縮前の熱伝導率×１００で表される数である。 Further, it is preferable that the present polysiloxane porous body undergoes little change in thermal conductivity even when it is deformed by compression from the outside. The rate of change in thermal conductivity is not particularly limited. The rate of change in thermal conductivity compared is preferably 10.0% or less, more preferably 6.0% or less.
The rate of change in thermal conductivity is the percentage of the ratio of the absolute value of the difference between the thermal conductivity after compression and the thermal conductivity before compression to the thermal conductivity before compression. That is, it is a number expressed by the formula: Change rate of thermal conductivity=|Thermal conductivity after compression−Thermal conductivity before compression|/Thermal conductivity before compression×100.
　また、上記熱伝導率の変化率は、圧縮率が０～６０％の範囲全体にわたって１０．０％以下であることが好ましく、６．０％以下であることがより好ましい。なお、熱伝導率の変化率は、小数第２位を四捨五入して求められる値とする。 In addition, the rate of change in thermal conductivity is preferably 10.0% or less, more preferably 6.0% or less, over the entire compressibility range of 0 to 60%. The rate of change in thermal conductivity is a value obtained by rounding off to the second decimal place.
（用途）
　本ポリシロキサン多孔体は優れた柔軟性、優れた耐熱性、及び、優れた断熱性等を有し、断熱材等として利用できる。
　また、液体窒素温度でも柔軟性を保つという特徴から、液体窒素を吸着させ、保持させる、液体窒素吸着材としても使用できる。 (Application)
The present polysiloxane porous body has excellent flexibility, excellent heat resistance, excellent heat insulating properties, etc., and can be used as a heat insulating material and the like.
In addition, it can be used as a liquid nitrogen adsorbent that adsorbs and retains liquid nitrogen because it retains its flexibility even at the temperature of liquid nitrogen.
　また、本ポリシロキサン多孔体は撥液性、及び、防汚性を有しており撥液基板等としても利用できる。また、水・油分離媒体、リポソーム作製、及び、防音防振材としても利用できる。
　更に、破砕することで、化粧料の添加物、樹脂充填剤（フィラー）、及び、反射材等としても利用できる。 In addition, the present polysiloxane porous body has liquid repellency and antifouling properties, and can be used as a liquid repellent substrate or the like. It can also be used as a water/oil separation medium, liposome preparation, and sound and vibration insulating material.
Furthermore, by crushing, it can be used as an additive for cosmetics, a resin filler (filler), a reflective material, and the like.
［保温容器］
　本発明の実施形態に係る保温容器は、本ポリシロキサン多孔体を含む保温材を備える保温容器である。
　以下では、本発明の実施形態に係る保温容器について図面を参照して説明する。以下に示す実施形態は、本発明の技術的思想を具体化した一例であって、本発明の技術的思想は、構成部品の材質、形状、構造、及び、配置等を下記の実施形態に特定するものではない。また、図面は模式的なものである。そのため、厚みと平面寸法との関係、比率等は現実のものとは異なる場合があり、また、図面相互間においても互いの寸法の関係や比率が異なることがある。 [Thermal container]
A heat insulating container according to an embodiment of the present invention is a heat insulating container provided with a heat insulating material containing the present polysiloxane porous material.
Below, the thermal insulation container which concerns on embodiment of this invention is demonstrated with reference to drawings. The embodiment shown below is an example embodying the technical idea of the present invention. not something to do. Also, the drawings are schematic. Therefore, the relationship, ratio, etc. between the thickness and the planar dimension may differ from the actual one, and the relationship and ratio of the dimension may differ between drawings.
　図２は、本発明の一実施形態に係る保温容器１の全体構成を示す斜視図である。図３は、保温容器１の断面図である。図４は、保温容器１の分解断面図である。図３及び図４は、保温容器１の径方向の中心をＸ－Ｙ面と平行な面で切断したときの断面図である。 FIG. 2 is a perspective view showing the overall configuration of the heat insulating container 1 according to one embodiment of the present invention. FIG. 3 is a cross-sectional view of the heat insulating container 1. As shown in FIG. FIG. 4 is an exploded sectional view of the heat insulating container 1. As shown in FIG. 3 and 4 are cross-sectional views taken along a plane parallel to the XY plane at the radial center of the heat insulating container 1. FIG.
　図２及び図３に示すように、保温容器１は、筐体１０、容器本体２０、保温材収納部３０、支持部材４０、保温材５０（図５参照）及び容器開閉部６０を備える。 As shown in FIGS. 2 and 3, the heat insulating container 1 includes a housing 10, a container body 20, a heat insulating material storage portion 30, a support member 40, a heat insulating material 50 (see FIG. 5), and a container opening/closing portion 60.
　保温容器１は、ヒト及び動物用の医薬品、医薬部外品、飲食品、並びに、試験研究用試薬等の温度管理を必要とする物品の運搬に用いられる保温容器である。保温容器１は、全体が円筒形となるように形成されている。 The heat-retaining container 1 is a heat-retaining container used for transporting goods that require temperature control, such as pharmaceuticals for humans and animals, quasi-drugs, food and drink, and test and research reagents. The heat insulating container 1 is formed in a cylindrical shape as a whole.
（筐体１０）
　筐体１０は、保温容器１の最も外側に配置される部材であり、図３に示すように、Ｘ－Ｙ面と平行な断面が凹形状に形成されている。
　筐体１０は、外表面１１と内表面１２との間に、真空断熱層１３が設けられている。真空断熱層１３は、大気圧よりも低い圧力の気体で満たされた層である。真空断熱層１３は、筐体１０の径方向（Ｘ方向）の側面及び筐体１０の下側（Ｙ２側）の底面において連通している。すなわち、真空断熱層１３は、筐体１０において、容器開閉部６０側を除いて凹形状となるように形成されている。筐体１０は、例えば、アルミニウム、及び、ステンレス鋼等の金属部材により形成されている。 (Case 10)
The housing 10 is the outermost member of the heat insulating container 1, and as shown in FIG. 3, has a concave cross section parallel to the XY plane.
The housing 10 is provided with a vacuum heat insulating layer 13 between the outer surface 11 and the inner surface 12 . The vacuum heat insulating layer 13 is a layer filled with gas having a pressure lower than atmospheric pressure. The vacuum heat insulating layer 13 communicates with the radial (X direction) side surface of the housing 10 and the lower (Y2 side) bottom surface of the housing 10 . That is, the vacuum heat insulating layer 13 is formed to have a concave shape in the housing 10 except for the container opening/closing part 60 side. The housing 10 is made of, for example, a metal member such as aluminum and stainless steel.
　また、図４に示すように、筐体１０の外表面１１において、上側（Ｙ１側）の端部には、ネジ部１１ｓが設けられている。ネジ部１１ｓは、後述する容器開閉部６０（開閉部本体６１）のネジ部６１ｓと係合する雄ネジである。 In addition, as shown in FIG. 4, the outer surface 11 of the housing 10 is provided with a threaded portion 11s at the end portion on the upper side (Y1 side). The threaded portion 11s is a male screw that engages with a threaded portion 61s of a container opening/closing portion 60 (opening/closing portion main body 61), which will be described later.
（容器本体２０）
　容器本体２０は、筐体１０の内表面１２の内側に設けられる部材であり、図３に示すように、Ｘ－Ｙ面と平行な断面が凹形状となるように形成されている。容器本体２０の内部には、図示しない保温対象物が収容される。容器本体２０の外径は、筐体１０の内径よりも小さく、筐体１０の内表面１２と容器本体２０の外表面２２との間に隙間ｇ１が形成される。この隙間ｇ１の空間には、保温材収納部３０（後述）が設けられる。 (Container body 20)
The container body 20 is a member provided inside the inner surface 12 of the housing 10, and as shown in FIG. 3, is formed so that the cross section parallel to the XY plane has a concave shape. An object to be kept warm (not shown) is accommodated inside the container body 20 . The outer diameter of container body 20 is smaller than the inner diameter of housing 10 , and gap g<b>1 is formed between inner surface 12 of housing 10 and outer surface 22 of container body 20 . A heat insulating material housing portion 30 (described later) is provided in the space of the gap g1.
　なお、後述する保温材を緩衝材として使用する場合、保温容器１は、この容器本体２０を有していなくてもよい。本ポリシロキサン多孔体は液体窒素を含浸した状態でもその柔軟性を失わないという特徴があり、極低温でも緩衝性を失わない。そのため、容器本体２０を有しない形態では、保温と緩衝との２つの機能を保温材が担う。この形態の保温容器については後述する。 It should be noted that the heat insulating container 1 does not have to have this container body 20 when a heat insulating material, which will be described later, is used as a cushioning material. The present polysiloxane porous material is characterized in that it does not lose its flexibility even when impregnated with liquid nitrogen, and does not lose its buffering properties even at extremely low temperatures. Therefore, in the form without the container main body 20, the heat insulating material has two functions of heat insulation and cushioning. A heat insulating container of this form will be described later.
　容器本体２０は、筐体１０と同じく、例えば、アルミニウム、及び、ステンレス鋼等の金属部材により形成されている。 Like the housing 10, the container body 20 is made of a metal member such as aluminum or stainless steel.
　容器本体２０は、筐体１０の内部において、支持部材４０により支持されている。支持部材４０は、筐体１０の底面１４と容器本体２０の底面２１との間を連結する部材である。容器本体２０を、支持部材４０で支持することにより、筐体１０の底面１４と容器本体２０の底面２１との間に隙間ｇ２が形成される。本実施形態の保温容器１において、隙間ｇ２の空間には保温材は配置されないが、支持部材４０を容器本体２０の側面に配置した場合、隙間ｇ２の空間に保温材５０を配置できる。なお、本実施形態では、図３に示すように、筐体１０の径方向（Ｘ方向）に沿って２つの支持部材４０を設けた例を示すが、支持部材４０の位置、個数は、適宜に設定される。 The container body 20 is supported by a support member 40 inside the housing 10 . The support member 40 is a member that connects the bottom surface 14 of the housing 10 and the bottom surface 21 of the container body 20 . A gap g2 is formed between the bottom surface 14 of the housing 10 and the bottom surface 21 of the container body 20 by supporting the container body 20 with the support member 40 . In the heat insulating container 1 of this embodiment, the heat insulating material is not arranged in the space of the gap g2, but when the support member 40 is arranged on the side surface of the container body 20, the heat insulating material 50 can be arranged in the space of the gap g2. In this embodiment, as shown in FIG. 3, an example in which two support members 40 are provided along the radial direction (X direction) of the housing 10 is shown. is set to
（保温材収納部３０）
　保温材収納部３０は、図３又は図４に示すように、筐体１０と容器本体２０との間に設けられた、円筒形の空間である。保温材収納部３０には、保温材５０が取り外し可能に収納される。図２～図４では、保温材５０を図示していない。保温材５０の構成については、後述する。 (Insulating material storage unit 30)
As shown in FIG. 3 or 4, the heat insulating material housing portion 30 is a cylindrical space provided between the housing 10 and the container body 20. As shown in FIG. A heat insulator 50 is detachably stored in the heat insulator storage portion 30 . 2 to 4 do not show the heat insulating material 50. FIG. A configuration of the heat insulating material 50 will be described later.
（容器開閉部６０）
　容器開閉部６０は、図４に示すように、容器本体２０の開口部２３及び保温材収納部３０の開口部３１を開放又は閉鎖する部材である。容器開閉部６０は、開閉部本体６１からなる。容器開閉部６０を構成する各部は、筐体１０と同じく金属部材により形成されてもよいし、プラスチック等の樹脂材料により形成されてもよい。
　開閉部本体６１は、筐体１０に着脱自在に取り付けられる部材であり、断面が略凸形状となるように形成されている。開閉部本体６１において、裏面側となるＹ２側の内周面には、ネジ部６１ｓが設けられている。ネジ部６１ｓは、筐体１０に設けられたネジ部１１ｓと係合する雌ネジである。 (Container opening/closing unit 60)
The container opening/closing part 60 is a member that opens or closes the opening 23 of the container body 20 and the opening 31 of the heat insulating material storage part 30, as shown in FIG. The container opening/closing part 60 is composed of an opening/closing part main body 61 . Each part constituting the container opening/closing part 60 may be made of a metal member like the housing 10, or may be made of a resin material such as plastic.
The opening/closing unit main body 61 is a member detachably attached to the housing 10, and is formed to have a substantially convex cross section. A screw portion 61s is provided on the inner peripheral surface of the opening/closing portion main body 61 on the Y2 side, which is the rear surface side. The threaded portion 61s is a female thread that engages with the threaded portion 11s provided on the housing 10 .
　筐体１０のネジ部１１ｓに対して、開閉部本体６１のネジ部６１ｓが係合するように開閉部本体６１を回転させることにより、開閉部本体６１を筐体１０に取り付けることができる。開閉部本体６１を筐体１０に取り付けることにより、図３に示すように、容器本体２０の開口部２３及び保温材収納部３０の開口部３１は、閉鎖される。また、開閉部本体６１を筐体１０から取り外すことにより、図４に示すように、容器本体２０の開口部２３及び保温材収納部３０の開口部３１は、開放される。 The opening/closing part main body 61 can be attached to the housing 10 by rotating the opening/closing part main body 61 so that the screw part 61s of the opening/closing part main body 61 is engaged with the screw part 11s of the housing 10 . By attaching the opening/closing unit main body 61 to the housing 10, the opening 23 of the container main body 20 and the opening 31 of the heat insulating material storage unit 30 are closed as shown in FIG. 4, the opening 23 of the container body 20 and the opening 31 of the heat insulating material storage part 30 are opened by removing the opening/closing part main body 61 from the housing 10. As shown in FIG.
（保温材）
　保温材は、本ポリシロキサン多孔体を含む。本ポリシロキサン多孔体は優れた断熱性を有するため、本ポリシロキサン多孔体を備える保温容器１は優れた保温性能を有する。 (Insulation material)
The heat insulating material contains the present polysiloxane porous body. Since the present polysiloxane porous material has excellent heat insulating properties, the heat insulating container 1 provided with the present polysiloxane porous material has excellent heat retaining performance.
　保温材は、更に、液体媒体を含んでいてもよい。本ポリシロキサン多孔体は優れた温度安定性と、連通したマクロ孔とを有しており、加温された液体媒体、又は、冷却された液体媒体を含浸させることで、容器内の温度を容易に制御できる。液体媒体としては、例えば、液体窒素等が挙げられる。 The heat insulating material may further contain a liquid medium. This polysiloxane porous material has excellent temperature stability and continuous macropores, and can easily adjust the temperature inside the container by impregnating it with a heated or cooled liquid medium. can be controlled to Examples of liquid media include liquid nitrogen.
　図５は、保温材５０の使用形態を示す斜視図である。図５では、保温材５０の長手方向を上下方向（Ｙ方向）として説明する。
　保温材５０は、本ポリシロキサン多孔体を含み、円筒形に構成されている。保温材５０の外径Ｄ１及び内径Ｄ２は、保温材５０を、保温材収納部３０の隙間ｇ１（図３参照）に収納可能な寸法に設定される。なお、保温材５０と保温材収納部３０との間には、隙間が生じていてもよい。 FIG. 5 is a perspective view showing how the heat insulating material 50 is used. In FIG. 5, the longitudinal direction of the heat insulating material 50 will be described as the vertical direction (Y direction).
The heat insulating material 50 includes the present polysiloxane porous body and has a cylindrical shape. The outer diameter D1 and the inner diameter D2 of the heat insulating material 50 are set so that the heat insulating material 50 can be accommodated in the gap g1 (see FIG. 3) of the heat insulating material accommodating portion 30. As shown in FIG. A gap may be formed between the heat insulating material 50 and the heat insulating material housing portion 30 .
　図６は、保温容器１における保温材５０の装着方法を説明する図である。
　保温材５０を保温材収納部３０（筐体１０）に収納するには、図６に示すように、筐体１０から容器開閉部６０を取り外して、保温材収納部３０の開口部３１を開放する。そして、保温材５０を、保温材収納部３０の開口部３１から挿入する。 6A and 6B are diagrams for explaining a method of attaching the heat insulating material 50 to the heat insulating container 1. FIG.
In order to store the heat insulating material 50 in the heat insulating material housing portion 30 (housing 10), as shown in FIG. do. Then, the heat insulating material 50 is inserted through the opening 31 of the heat insulating material housing portion 30 .
　次に、筐体１０のネジ部１１ｓと、開閉部本体６１（容器開閉部６０）のネジ部６１ｓとを係合させ、開閉部本体６１を回転させることにより、容器開閉部６０を筐体１０に取り付けることができる。 Next, the screw portion 11 s of the housing 10 and the screw portion 61 s of the opening/closing portion main body 61 (container opening/closing portion 60 ) are engaged with each other, and the opening/closing portion main body 61 is rotated to move the container opening/closing portion 60 to the housing 10 . can be attached to
　保温容器１において、容器本体２０は、筐体１０の底面１４と容器本体２０の底面２１との間を連結する支持部材４０により支持されている。そのため、保温容器１は、筐体１０の内部において、容器本体２０をより安定して保持できる。 In the heat insulating container 1 , the container body 20 is supported by a support member 40 that connects the bottom surface 14 of the housing 10 and the bottom surface 21 of the container body 20 . Therefore, the heat insulating container 1 can more stably hold the container body 20 inside the housing 10 .
　図７は、保温容器の変形例である。保温容器２は、保温容器１が有していた容器本体２０を有さず、底部を有する円筒状の保温材５０を有している。保温容器２では、保温対象物は保温材５０に直接触れる状態で保持される。すでに説明したとおり、保温材５０は優れた柔軟性を有しているため緩衝材としても機能する。 Fig. 7 is a modification of the heat insulating container. The heat insulating container 2 does not have the container body 20 that the heat insulating container 1 has, but has a cylindrical heat insulating material 50 having a bottom. In the heat insulating container 2, the heat insulating object is held in direct contact with the heat insulating material 50. - 特許庁As already explained, the heat insulating material 50 has excellent flexibility and thus functions as a cushioning material.
　保温容器２は、保温容器１と比較して保温材５０の厚みが大きくなっている。これにより、保温性がより高くなることはもとより、保温材５０による緩衝性能が高められている。
　保温容器２の厚みは適宜定められればよいが、例えば、保温対象物が、ぴったりと嵌め合わされるような形態になるよう、調整されてもよい。すなわち、保温対象物が筒状であれば、その筒がぴったり収まるよう、保温材５０の厚みを調整すればよい。 In the heat insulating container 2, the thickness of the heat insulating material 50 is larger than that of the heat insulating container 1. - 特許庁As a result, not only is the heat retaining property higher, but also the cushioning performance of the heat retaining material 50 is enhanced.
The thickness of the heat-retaining container 2 may be determined as appropriate, but may be adjusted, for example, so that the object to be heat-retained fits tightly. That is, if the object to be kept warm is cylindrical, the thickness of the heat insulating material 50 should be adjusted so that the cylinder fits perfectly.
　また、保温材５０に液体窒素等を含浸させれば、保温容器２の内部を低温に保持しつつ、保温材５０による緩衝機能は失われず、低温での運搬が必要な医薬品等の運搬に好ましく用いることができる。 In addition, if the heat insulating material 50 is impregnated with liquid nitrogen or the like, the inside of the heat insulating container 2 can be maintained at a low temperature without losing the buffering function of the heat insulating material 50, which is preferable for transporting medicines and the like that need to be transported at low temperatures. can be used.
　また、本ポリシロキサン多孔体は、優れた柔軟性を有しつつ、圧縮による熱伝導率の変化も小さいため、保温材５０のような成形品でなくても、隙間を埋めるような形態で押し込んで使用した場合でも、優れた保温効果（断熱効果）が得られるという特徴を有している。 In addition, the present polysiloxane porous body has excellent flexibility and little change in thermal conductivity due to compression. It has the characteristic that excellent heat retention effect (insulation effect) can be obtained even when used in .
　以下、実施例により、本発明をさらに詳細に説明する。本発明は、以下に示す実施例に限定されない。 The present invention will be described in more detail below with reference to examples. The invention is not limited to the examples shown below.
（ポリシロキサン多孔体の作製）
　５ｍＭ酢酸１５ｍＬに尿素５ｇを溶かし、表１に記載した組成となるよう、テトラメトキシシラン（ＴＭＯＳ）、メチルトリメトキシシラン（ＭＴＭＳ）、ジメチルジメトキシシラン（ＤＭＤＭＳ）を滴下して１５分間攪拌し、組成物を調製した。 (Preparation of polysiloxane porous body)
Dissolve 5 g of urea in 15 mL of 5 mM acetic acid, add tetramethoxysilane (TMOS), methyltrimethoxysilane (MTMS), and dimethyldimethoxysilane (DMDMS) dropwise so as to obtain the composition shown in Table 1, and stir for 15 minutes. prepared the product.
　組成物を密閉容器（ゲル型）に移し８０℃で２４時間保温し、反応（ゲル化・エージング）を行なった。 The composition was transferred to an airtight container (gel type) and kept at 80°C for 24 hours for reaction (gelation/aging).
　得られたゲルを型から外し、５倍量以上の純水で１回、工業アルコールで２回、それぞれ６時間以上の浸漬洗浄を行なった後、６０℃で蒸発乾燥し、乾燥状態の硬化物（ポリシロキサン多孔体）を得た。 The resulting gel was removed from the mold, washed once with 5 or more volumes of pure water and twice with industrial alcohol for at least 6 hours each, and then evaporated to dryness at 60°C to obtain a cured product in a dry state. (Polysiloxane porous body) was obtained.
（評価１：硬化物の均質性）
　上記の手順により、均質な硬化物が得られた組成物については、表１の「評価１」欄に「Ａ」が記載されている。一方、均質な硬化物が得られなかった組成物については、「評価１」欄に「Ｂ」が記載されている。 (Evaluation 1: Homogeneity of cured product)
"A" is described in the "Evaluation 1" column of Table 1 for the composition from which a homogeneous cured product was obtained by the above procedure. On the other hand, "B" is described in the "Evaluation 1" column for the compositions for which a homogeneous cured product was not obtained.
（評価２：硬化物の耐屈曲性）
　次に、得られた硬化物（厚み：５ｍｍ）を直径１０ｍｍの円柱（棒）に巻き付け、クラックが生じるかを観察した。得られた硬化物にクラックが生じなかった組成物については、得られた硬化物は、「ポリシロキサン多孔体（マシュマロゲル）」と認められ、「評価２」欄に「Ａ」が記載されている。一方、クラックが生じ、得られた硬化物が所望の耐屈曲性を有していなかった組成物は、「評価２」欄に「Ｂ」が記載されている。
　なお、均質な硬化物が得られなかった組成物については、上記試験を実施することができなかったので、「－」が記載されている。 (Evaluation 2: bending resistance of cured product)
Next, the obtained cured product (thickness: 5 mm) was wound around a cylinder (rod) with a diameter of 10 mm, and it was observed whether cracks were generated. For the compositions in which no cracks occurred in the obtained cured product, the obtained cured product was recognized as a "polysiloxane porous body (marshmallow gel)", and "A" was entered in the "Evaluation 2" column. there is On the other hand, "B" is described in the "Evaluation 2" column for compositions in which cracks occurred and the resulting cured product did not have the desired flex resistance.
In addition, since the above test could not be carried out for compositions for which a homogeneous cured product could not be obtained, "-" is indicated.
　図８は、三角図に各組成物をプロットしたものである。上記評価がいずれも「Ａ」であったもの（マシュマロゲル）を「●（中黒円）」とし、評価１が「Ａ」で評価２が「Ｂ」であったものを「〇（中白円）」とし、評価１が「Ｂ」であったものを「△（中白三角）」とした。
　なお、図８中「●」の組成物により得られたポリシロキサン多孔体は、ポリシロキサンから構成された骨格と、マクロ孔との共連続構造とを有するシリコーン組成のモノリス型マクロ多孔性部材（マシュマロゲル）であった。一方、「〇」及び「△」はマシュマロゲルではなかった。 FIG. 8 plots each composition in a ternary diagram. Those for which the above evaluations were all "A" (marshmallow gel) were designated as "● (middle black circle)", and those for which evaluation 1 was "A" and evaluation 2 was "B" were designated as "○ (middle white) Yen)”, and the evaluation 1 was “B” was designated as “△ (white triangle)”.
The polysiloxane porous material obtained from the composition indicated by "●" in FIG. 8 is a monolithic macroporous member ( marshmallow gel). On the other hand, "◯" and "△" were not marshmallow gels.
　評価１、及び、評価２がいずれも「Ａ」であったポリシロキサン多孔体については、上記の各原料を５倍量としたことを除いては上記と同様の方法で再度合成を行い、約１１０ｍｍ×１１０ｍｍ×１０ｍｍのパネルを作成して、以下の方法により、熱伝導率を測定した。表２はその結果である。 For the polysiloxane porous bodies for which both evaluation 1 and evaluation 2 were "A", synthesis was performed again in the same manner as described above, except that the amount of each of the above raw materials was increased to 5 times. A panel of 110 mm x 110 mm x 10 mm was produced, and thermal conductivity was measured by the following method. Table 2 is the result.
（熱伝導率測定）
　熱伝導率は、ＮＥＴＺＳＣＨ（ネッチ）社の「ＨＦＭ４４６Ｌａｍｂｄａ」の「ｓｍａｌｌ」を用いて熱流計法（ＡＳＴＭ　Ｃ５１８）で実施した。上板の温度を２５℃（高温側）、下板の温度を１５℃（低温側）として、この２枚の板の間に試料を挟持して圧縮応力を印加しながら熱伝導率を測定した。なお、試験は上下の板の中間温度である２０℃で実施した。
　試料は、マシュマロゲルの厚み約１０ｍｍのパネル（大きさ１１０ｍｍ×１１０ｍｍ）とした。 (Thermal conductivity measurement)
Thermal conductivity was measured by a heat flow meter method (ASTM C518) using "small" of "HFM446 Lambda" from NETZSCH. The temperature of the upper plate was set at 25° C. (high temperature side) and the temperature of the lower plate was set at 15° C. (low temperature side), and the thermal conductivity was measured while the sample was sandwiched between the two plates and a compressive stress was applied. The test was conducted at 20°C, which is the intermediate temperature between the upper and lower plates.
The sample was a marshmallow gel panel with a thickness of about 10 mm (size: 110 mm x 110 mm).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の結果から、ケイ素アルコキシドの含有量が、
１０．５モル％≦ＴＥＡＳ　≦２０．０モル％、かつ、
１１．０モル％≦ＤＭＤＡＳ≦４１．０モル％である、例１～９の組成物を用いると、優れた柔軟性を有する均質なポリシロキサン多孔体が得られることがわかった。
　一方、上記範囲外である、例１０～例２５の組成物を用いると、均質なポリシロキサン多孔体（乾燥体）が得られないか、又は、ポリシロキサン多孔体が得られたとしても共連続のマクロ孔を有さず、所望の柔軟性を有していなかった（マシュマロゲルは得られなかった）。 From the results in Table 1, the content of silicon alkoxide is
10.5 mol% ≤ TEAS ≤ 20.0 mol%, and
It was found that using the compositions of Examples 1-9, where 11.0 mol %≦DMDAS≦41.0 mol %, yields homogeneous polysiloxane porous bodies with excellent flexibility.
On the other hand, when the compositions of Examples 10 to 25, which are outside the above range, are used, a homogeneous polysiloxane porous body (dry body) cannot be obtained, or even if a polysiloxane porous body is obtained, it is co-continuous. macropores and did not have the desired flexibility (no marshmallow gel was obtained).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２の結果から、ケイ素アルコキシドの含有量が、
１０．５モル％≦ＴＥＡＳ　≦２０．０モル％、
１１．０モル％≦ＤＭＤＡＳ≦３８．０モル％、かつ、
３９．０モル％≦ＭＴＡＳ　≦７８．５モル％、
の範囲内である、例２の組成物のポリシロキサン多孔体は、上記範囲外である例１の組成物のポリシロキサン多孔体よりも、より低い熱伝導率（より高い断熱性）を有していることがわかった。 From the results in Table 2, the content of silicon alkoxide is
10.5 mol% ≤ TEAS ≤ 20.0 mol%,
11.0 mol% ≤ DMDAS ≤ 38.0 mol%, and
39.0 mol%≤MTAS≤78.5 mol%,
The polysiloxane porous body of the composition of Example 2, which is within the above range, has a lower thermal conductivity (higher heat insulation) than the polysiloxane porous body of the composition of Example 1, which is outside the above range. It turns out that
　また、ケイ素アルコキシドの含有量が、
１７．０モル％≦ＴＥＡＳ　≦２０．０モル％、
１１．０モル％≦ＤＭＤＡＳ≦３８．０モル％、かつ、
３９．０モル％≦ＭＴＡＳ　≦５０モル％
の範囲内である、例２の組成物のポリシロキサン多孔体は、上記範囲外である例４の組成物のポリシロキサン多孔体よりも、更に低い熱伝導率（更に高い断熱性）を有していることがわかった。 Also, the content of silicon alkoxide is
17.0 mol% ≤ TEAS ≤ 20.0 mol%,
11.0 mol% ≤ DMDAS ≤ 38.0 mol%, and
39.0 mol% ≤ MTAS ≤ 50 mol%
The polysiloxane porous body of the composition of Example 2, which is within the range of, has a lower thermal conductivity (higher heat insulation) than the polysiloxane porous body of the composition of Example 4, which is outside the above range. It turns out that
　また、ケイ素アルコキシドの含有量が、
１０．５モル％≦ＴＥＡＳ　≦２０．０モル％、
１１．０モル％≦ＤＭＤＡＳ≦３８．０モル％、かつ、
６７．０モル％≦ＭＴＡＳ　≦７８．５モル％
の範囲内である、例５の組成物のポリシロキサン多孔体は、上記範囲外である例４の組成物のポリシロキサン多孔体よりも、更に低い熱伝導率（更に高い断熱性）を有していることがわかった。 Also, the content of silicon alkoxide is
10.5 mol% ≤ TEAS ≤ 20.0 mol%,
11.0 mol% ≤ DMDAS ≤ 38.0 mol%, and
67.0 mol% ≤ MTAS ≤ 78.5 mol%
The polysiloxane porous body of the composition of Example 5, which is within the range of, has a lower thermal conductivity (higher heat insulation) than the polysiloxane porous body of the composition of Example 4, which is outside the above range. It turns out that
（ポリシロキサン多孔体の作製２）
　組成物中における５ｍＭ酢酸、及び、尿素の含有量を以下の表３に記載したとおりとしたことを除いては表１の例３と同様にしてポリシロキサン多孔体を作製した。その結果、いずれも優れた柔軟性（耐屈曲性評価「Ａ」）を有するポリシロキサン多孔体（マシュマロゲル）が得られた。また、上記と同様の方法で熱伝導率、及び、かさ密度を測定した。表３はその結果である。 (Preparation of polysiloxane porous body 2)
A polysiloxane porous body was produced in the same manner as Example 3 in Table 1, except that the contents of 5 mM acetic acid and urea in the composition were as shown in Table 3 below. As a result, a polysiloxane porous body (marshmallow gel) having excellent flexibility (flex resistance evaluation "A") was obtained. Also, thermal conductivity and bulk density were measured in the same manner as above. Table 3 is the result.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　次に、例３－Ｃのマシュマロゲルについて、一軸圧縮を加えて圧縮率を変化させながら、上記と同様にして、熱伝導率を測定した。表４はその結果である。 Next, the thermal conductivity of the marshmallow gel of Example 3-C was measured in the same manner as above while uniaxial compression was applied to change the compression rate. Table 4 is the result.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４の結果から、本ポリシロキサン多孔体は、圧縮による熱伝導率の変化が小さいことが分かった。
　また、無圧縮（例３－Ｃ）の熱伝導率と比較したとき、圧縮率が６１．０％のときの熱伝導率の変化率は３．３％以下であった。また、圧縮率０～６１．０％の範囲にわたって、熱伝導率の変化率は１０．０％以下であり、６．０％以下であった。 From the results in Table 4, it was found that the present polysiloxane porous body had little change in thermal conductivity due to compression.
In addition, when compared with the thermal conductivity of the uncompressed sample (Example 3-C), the rate of change in thermal conductivity was 3.3% or less when the compressibility was 61.0%. Moreover, the rate of change in thermal conductivity was 10.0% or less and 6.0% or less over the range of compressibility from 0 to 61.0%.
　本製造方法によれば、優れた柔軟性を有するポリシロキサン多孔体を、界面活性剤を用いなくても得ることができる。従来、同様のポリシロキサン多孔体を得るためには界面活性剤の使用が必須と考えられており、この除去には多量の有機溶剤による洗浄が必要であり、環境負荷が大きかった。本製造方法は上記の課題を解決するものである。 According to this production method, a polysiloxane porous body having excellent flexibility can be obtained without using a surfactant. Conventionally, it has been considered essential to use a surfactant in order to obtain a similar polysiloxane porous material, and its removal requires washing with a large amount of organic solvent, which has a large environmental impact. This manufacturing method solves the above problems.
　また本製造方法により得られるポリシロキサン多孔体は優れた柔軟性、優れた耐熱性、及び、優れた断熱性等を有し、断熱材等として利用できる。
　また、液体窒素温度でも柔軟性を保つという特徴から、液体窒素を吸着させ、保持させる、液体窒素吸着材としても使用できる。 Moreover, the polysiloxane porous material obtained by this production method has excellent flexibility, excellent heat resistance, excellent heat insulating properties, etc., and can be used as a heat insulating material.
In addition, it can be used as a liquid nitrogen adsorbent that adsorbs and retains liquid nitrogen because it retains its flexibility even at the temperature of liquid nitrogen.
　また、本ポリシロキサン多孔体は撥液性、及び、防汚性を有しており撥液基板等としても利用できる。また、水・油分離媒体、リポソーム作製、及び、防音防振材としても利用できる。
　更に、破砕することで、化粧料の添加物、樹脂充填剤（フィラー）、及び、反射材等としても利用できる。 In addition, the present polysiloxane porous body has liquid repellency and antifouling properties, and can be used as a liquid repellent substrate or the like. It can also be used as a water/oil separation medium, liposome preparation, and sound and vibration insulating material.
Furthermore, by crushing, it can be used as an additive for cosmetics, a resin filler (filler), a reflective material, and the like.
１、２　　　：保温容器
１０　　：筐体
１１　　：外表面
１１ｓ　：ネジ部
１２　　：内表面
１３　　：真空断熱層
１４　　：底面
２０　　：容器本体
２１　　：底面
２２　　：外表面
２３　　：開口部
３０　　：保温材収納部
３１　　：開口部
４０　　：支持部材
５０　　：保温材
６０　　：容器開閉部
６１　　：開閉部本体
６１ｓ　：ネジ部 1, 2: Thermal insulation container 10: Housing 11: Outer surface 11s: Threaded portion 12: Inner surface 13: Vacuum insulation layer 14: Bottom surface 20: Container main body 21: Bottom surface 22: Outer surface 23: Opening 30: Heat insulating material storage Portion 31: opening 40: support member 50: heat insulating material 60: container opening/closing portion 61: opening/closing portion main body 61s: screw portion

Claims (15)

  1. 　テトラアルコキシシランと、メチルトリアルコキシシランと、ジメチルジアルコキシシランと、水とを含む組成物を調製し、ゲル化させてゲルを形成することと、
    　前記ゲルを乾燥させてポリシロキサン多孔体を得ることと、を含み、
    　前記組成物中における前記テトラアルコキシシランと、前記メチルトリアルコキシシランと、前記ジメチルジアルコキシシランの含有量の合計を１００モル％としたとき、前記テトラアルコキシシランの含有量が、１０．５～２０．０モル％であり、前記ジメチルジアルコキシシランの含有量が１１．０～４１．０モル％である、ポリシロキサン多孔体の製造方法。     preparing and gelling a composition comprising tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, and water to form a gel;
    drying the gel to obtain a polysiloxane porous body,
    When the total content of the tetraalkoxysilane, the methyltrialkoxysilane, and the dimethyldialkoxysilane in the composition is 100 mol%, the content of the tetraalkoxysilane is 10.5 to 20. 0 mol %, and the content of the dimethyldialkoxysilane is 11.0 to 41.0 mol %.
  2. 　前記組成物が、界面活性剤を含まない、請求項１に記載のポリシロキサン多孔体の製造方法。 The method for producing a polysiloxane porous body according to claim 1, wherein the composition does not contain a surfactant.
  3. 　前記ジメチルジアルコキシシランの含有量が３８．０モル％以下である、請求項１又は２に記載のポリシロキサン多孔体の製造方法。 The method for producing a polysiloxane porous body according to claim 1 or 2, wherein the content of said dimethyldialkoxysilane is 38.0 mol% or less.
  4. 　前記メチルトリアルコキシシランの含有量が５０．０モル％以上であって、前記テトラアルコキシシランの含有量が１７．０モル％以上である、請求項３に記載のポリシロキサン多孔体の製造方法。 The method for producing a polysiloxane porous body according to claim 3, wherein the content of said methyltrialkoxysilane is 50.0 mol% or more and the content of said tetraalkoxysilane is 17.0 mol% or more.
  5. 　前記メチルトリアルコキシシランの含有量が６７．０モル％以上である、請求項３に記載のポリシロキサン多孔体の製造方法。 The method for producing a polysiloxane porous body according to claim 3, wherein the content of said methyltrialkoxysilane is 67.0 mol% or more.
  6. 　前記ポリシロキサン多孔体のかさ密度が０．３００ｇｃｍ－３以下である、請求項１～５のいずれか１項に記載のポリシロキサン多孔体の製造方法。 The method for producing a polysiloxane porous body according to any one of claims 1 to 5, wherein the polysiloxane porous body has a bulk density of 0.300 gcm -3 or less.
  7. 　２０℃における熱伝導率が０．０４００Ｗ／（ｍ・Ｋ）以下である、請求項１～６のいずれか１項に記載のポリシロキサン多孔体の製造方法。 The method for producing a polysiloxane porous body according to any one of claims 1 to 6, wherein the thermal conductivity at 20°C is 0.0400 W/(m·K) or less.
  8. 　テトラアルコキシシランと、メチルトリアルコキシシランと、ジメチルジアルコキシシランと、水とを含む組成物を加水分解縮合させて得られるポリシロキサン多孔体であって、前記組成物中における前記テトラアルコキシシランと、前記メチルトリアルコキシシランと、前記ジメチルジアルコキシシランの含有量の合計を１００モル％としたとき、前記テトラアルコキシシランの含有量が、１０．５～２０．０モル％であり、前記ジメチルジアルコキシシランの含有量が１１．０～４１．０モル％である、ポリシロキサン多孔体。 A polysiloxane porous body obtained by hydrolytic condensation of a composition containing tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, and water, wherein the tetraalkoxysilane in the composition, When the total content of the methyltrialkoxysilane and the dimethyldialkoxysilane is 100 mol%, the content of the tetraalkoxysilane is 10.5 to 20.0 mol%, and the dimethyldialkoxysilane A polysiloxane porous body having a silane content of 11.0 to 41.0 mol %.
  9. 　前記組成物中における前記ジメチルジアルコキシシランの含有量が３８．０モル％以下である、請求項８に記載のポリシロキサン多孔体。 The polysiloxane porous body according to claim 8, wherein the content of said dimethyldialkoxysilane in said composition is 38.0 mol% or less.
  10. 　前記組成物中における、前記メチルトリアルコキシシランの含有量が５０．０モル％以上であって、前記テトラアルコキシシランの含有量が１７．０モル％以上である、請求項９に記載のポリシロキサン多孔体。 10. The polysiloxane according to claim 9, wherein the content of the methyltrialkoxysilane in the composition is 50.0 mol% or more and the content of the tetraalkoxysilane is 17.0 mol% or more. Porous body.
  11. 　前記組成物中における、前記メチルトリアルコキシシランの含有量が６７．０モル％以上である、請求項９に記載のポリシロキサン多孔体。 The polysiloxane porous body according to claim 9, wherein the content of said methyltrialkoxysilane in said composition is 67.0 mol% or more.
  12. 　かさ密度が０．３００ｇｃｍ－３以下である、請求項８～１１のいずれか１項に記載のポリシロキサン多孔体。 The polysiloxane porous body according to any one of claims 8 to 11, which has a bulk density of 0.300 gcm -3 or less.
  13. 　２０℃における熱伝導率が０．０４００Ｗ／（ｍ・Ｋ）以下である、請求項８～１２のいずれか１項に記載のポリシロキサン多孔体。 The polysiloxane porous body according to any one of claims 8 to 12, which has a thermal conductivity of 0.0400 W/(m·K) or less at 20°C.
  14. 　請求項８～１３のいずれか１項に記載のポリシロキサン多孔体を含む保温材。 A heat insulating material containing the polysiloxane porous material according to any one of claims 8 to 13.
  15. 　請求項１４に記載の保温材を備える保温容器。 A heat insulating container comprising the heat insulating material according to claim 14.
PCT/JP2021/045943 2021-01-26 2021-12-14 Method for producing polysiloxane porous body, polysiloxane porous body, heat-insulating material, and heat-insulating container WO2022163178A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08165114A (en) * 1994-12-13 1996-06-25 Yamamura Glass Co Ltd Production of transparent silica gel bulk substance containing methyl group
CN104194028A (en) * 2014-08-15 2014-12-10 中国科学院新疆理化技术研究所 Preparation method and application of three-element siloxane sponge
WO2018062504A1 (en) * 2016-09-30 2018-04-05 国立研究開発法人科学技術振興機構 Composite material, gas adsorbent and method for producing composite material
JP2020193316A (en) * 2019-05-27 2020-12-03 ティエムファクトリ株式会社 Aerogel composite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08165114A (en) * 1994-12-13 1996-06-25 Yamamura Glass Co Ltd Production of transparent silica gel bulk substance containing methyl group
CN104194028A (en) * 2014-08-15 2014-12-10 中国科学院新疆理化技术研究所 Preparation method and application of three-element siloxane sponge
WO2018062504A1 (en) * 2016-09-30 2018-04-05 国立研究開発法人科学技術振興機構 Composite material, gas adsorbent and method for producing composite material
JP2020193316A (en) * 2019-05-27 2020-12-03 ティエムファクトリ株式会社 Aerogel composite

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