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WO2018097106A1 - Gel de polysiloxane ainsi que procédé de fabrication de celui-ci, matériau d'isolation thermique, et verre feuilleté - Google Patents

Gel de polysiloxane ainsi que procédé de fabrication de celui-ci, matériau d'isolation thermique, et verre feuilleté Download PDF

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WO2018097106A1
WO2018097106A1 PCT/JP2017/041702 JP2017041702W WO2018097106A1 WO 2018097106 A1 WO2018097106 A1 WO 2018097106A1 JP 2017041702 W JP2017041702 W JP 2017041702W WO 2018097106 A1 WO2018097106 A1 WO 2018097106A1
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polysiloxane
chain
group
skeleton
polymer
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PCT/JP2017/041702
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Japanese (ja)
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室伏　英伸
千恵子 室伏
山田　和彦
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旭硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences

Definitions

  • the present invention relates to a polysiloxane gel, a method for producing the same, a heat insulating material, and a laminated glass.
  • Transparent insulation is expected as insulation for automotive window glass and building window glass for the purpose of improving the cooling and heating efficiency of automobiles and buildings.
  • an alkylsiloxane airgel having a three-dimensional network structure formed from through-holes continuous in a three-dimensional network and a skeleton continuous in a three-dimensional network made of alkylsiloxane has been proposed.
  • Patent Document 1 an alkylsiloxane airgel having a three-dimensional network structure formed from through-holes continuous in a three-dimensional network and a skeleton continuous in a three-dimensional network made of alkylsiloxane has been proposed.
  • Examples of the material for the transparent heat insulating material include flexible polysiloxane airgel or xerogel.
  • the flexible polysiloxane airgel or xerogel for example, the following are proposed.
  • these silanes are copolymerized by sol-gel reaction to form a network of Si-O bonds.
  • an airgel or xerogel silicone monolith having a continuous through channel and a silicone skeleton capable of dissolving chemical species (Patent Document 2).
  • a polysiloxane porous body in which a liquid repellent group is bonded and the contact angle of n-hexadecane on the surface of the porous body is 150 ° or more (Patent Document 3).
  • the alkylsiloxane airgel of Patent Document 1 is brittle and cannot be bent. For this reason, the alkylsiloxane airgel of Patent Document 1 is easily broken when a force in the bending direction is applied, and is not convenient. Moreover, it is weak also to a tension
  • the present invention relates to a polysiloxane gel having a large bending fracture strain and a tensile fracture strain; a method capable of producing a polysiloxane gel having a large flexural fracture strain and a tensile fracture strain; a heat insulating material having a high thermal insulation property and being difficult to tear; and a high thermal insulation property. And the laminated glass which a tear is hard to produce in a transparent heat insulation layer is provided.
  • the polysiloxane gel of the present invention includes a three-dimensional network structure having an organic polymer skeleton having at least one polymer chain selected from the group consisting of a polyether chain, a polyester chain, and a polycarbonate chain, and a polysiloxane skeleton.
  • the method for producing a polysiloxane gel of the present invention comprises a three-dimensional network structure having an organic polymer skeleton having at least one polymer chain selected from the group consisting of a polyether chain, a polyester chain and a polycarbonate chain, and a polysiloxane skeleton.
  • a silyl group-containing polymer having an organic polymer skeleton having at least one polymer chain selected from the group consisting of a polyether chain, a polyester chain, and a polycarbonate chain, and a hydrolyzable silyl group And a solvent containing the solvent are gelled to obtain a wet gel.
  • the heat insulating material of the present invention includes the polysiloxane gel of the present invention.
  • the laminated glass of the present invention comprises a first glass plate, a second glass plate, and a transparent heat insulation layer existing between the first glass plate and the second glass plate, and the transparent heat insulation.
  • the layer is the polysiloxane gel of the present invention.
  • the polysiloxane gel of the present invention has a large bending fracture strain and tensile fracture strain. According to the method for producing a polysiloxane gel of the present invention, a polysiloxane gel having a large bending fracture strain and tensile fracture strain can be produced.
  • the heat insulating material of the present invention has high heat insulating properties, flexibility, and is difficult to tear off.
  • the laminated glass of the present invention has high heat insulating properties, the transparent heat insulating layer has flexibility, and the transparent heat insulating layer is not easily broken.
  • FIG. 1 is a cross-sectional view showing an example of the laminated glass of the present invention.
  • polysiloxane gel means a gel including a three-dimensional network structure having a polysiloxane skeleton in which siloxane bonds (Si—O—Si) are continuous.
  • Polysiloxane gels include wet gels with swelling agents (solvents) and xerogels without swelling agents.
  • Wet gel means a gel in which a three-dimensional network structure is swollen by a swelling agent. It includes hydrogels in which the swelling agent is water, alcogels in which the swelling agent is alcohol, and organogels in which the swelling agent is an organic solvent.
  • Xerogel is the definition of terminology related to the structure and process of sols, gels, meshes, and inorganic-organic composite materials by the International Union of Applied Chemistry (IUPAC) Inorganic Chemistry and Polymer Subcommittee "IUPAC recommendation 2007)" means "a gel composed of an open network formed by removing a swelling agent from a gel.”
  • IUPAC International Union of Applied Chemistry
  • IUPAC recommendation 2007 means "a gel composed of an open network formed by removing a swelling agent from a gel.”
  • the air-gel is the one from which the swelling agent has been removed by supercritical drying
  • the airgel is the one from which the swelling agent has been removed by normal evaporation drying
  • the cryogel is the one from which the swelling agent has been removed by freeze-drying. In the claims, these are collectively referred to as xerogel.
  • Transparent means that light can be transmitted.
  • the “bending fracture strain” is a value measured in accordance with JIS K 7171: 2008 “Plastics—How to obtain bending characteristics” (ISO 178: 2001).
  • “Tensile fracture strain” is a value measured in accordance with JIS K 7161: 1994 “Plastics—Testing method of tensile properties” (ISO 5271: 1993).
  • “Transmittance” is a value measured in accordance with JIS R 3106: 1998 “Testing method for transmittance, reflectance, emissivity, and solar heat gain of plate glass” (ISO 9050: 1990).
  • Thermal conductivity conforms to JIS A 1412-2: 1999 “Measurement method of thermal resistance and thermal conductivity of thermal insulation materials—Part 2: Heat flow meter method (HFM method)” (ISO 8301: 1991). Is a measured value.
  • the “average pore diameter” is a median diameter that is generally 50% higher than the integrated pore volume plot of the BJH (Barrett-Joyner-Halenda) adsorption by the measurement of the nitrogen adsorption method using a pore distribution measuring device. It is the value of the pore diameter called.
  • the “compressive modulus” is a value measured in accordance with JIS K 7181: 2011 “Plastics—How to obtain compression properties” (ISO 604: 2002).
  • the polysiloxane gel of the present invention includes a three-dimensional network structure having a specific organic polymer skeleton and a polysiloxane skeleton.
  • the polysiloxane gel of the present invention may be a wet gel containing a solvent or a xerogel containing no solvent.
  • the organic polymer backbone has a specific polymer chain.
  • the organic polymer skeleton may further have a first linking group interposed between the first end of the polymer chain and the polysiloxane skeleton.
  • the organic polymer skeleton further has a second linking group interposed between the second end of the polymer chain and the polysiloxane skeleton, or a chain linking group connecting between the second ends of the plurality of polymer chains. You may do it.
  • the organic polymer skeleton has a plurality of bonds, and at least two of the plurality of bonds are preferably bonded to the polysiloxane skeleton, and at least three of the plurality of bonds have More preferably, it is bonded to a polysiloxane skeleton.
  • the organic polymer skeleton becomes a branch point of the three-dimensional network structure, and the bending fracture strain and the tensile fracture strain of the polysiloxane gel are further increased.
  • the average molecular weight of one polymer chain is preferably 250 or more, more preferably 500 or more, and further preferably 1000 or more.
  • the polymer chain in the organic polymer skeleton is at least one selected from the group consisting of a polyether chain, a polyester chain, and a polycarbonate chain.
  • the organic polymer skeleton may have a plurality of types of polymer chains.
  • a polyether chain is preferable from the viewpoint of easy production or availability of a silyl group-containing polymer as a raw material.
  • Polyether chain e.g., - (OR 11) a - is represented by.
  • R 11 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and a is an integer of 2 or more.
  • -(OR 11 ) a- may be composed of a plurality of types of OR 11 having different carbon numbers for R 11 .
  • - (OR 11) a - if is composed of a plurality of kinds of OR 11, the arrangement of the OR 11 are random, alternating, may be any of block.
  • R 11 is, for example, a residue derived from an alkylene oxide described later.
  • R 11 is preferably an alkylene group.
  • — (OR 11 ) a — includes — (OCH 2 CH 2 ) a —, — (OCH 2 CH (CH 3 )) a —, — (OCH 2 CH 2 CH 2 CH 2 ) a —, — (OCH 2 CH 2 ) a1 (OCH 2 CH (CH 3 )) a2 -,-(OCH 2 CH 2 ) a1 (OCH 2 CH 2 CH 2 CH 2 ) a2- and the like.
  • Some hydrogen atoms may be substituted with fluorine or chlorine atoms.
  • each of a1 and a2 is an integer of 1 or more, and the total of a1 and a2 is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.
  • the average molecular weight of one polyether chain is preferably 250 or more, more preferably 500 or more, and further preferably 1000 or more.
  • Polyester chains are, for example, —O—R 21 — (OC (O) R 22 C (O) OR 21 ) c —, — (OC (O) R 22 C (O) OR 21 ) c —, or — ( OC (O) R 23 ) e-
  • R 21 , R 22 and R 23 are each a divalent hydrocarbon group having 1 to 12 carbon atoms, and c and e are each an integer of 2 or more. Some hydrogen atoms may be substituted with fluorine or chlorine atoms.
  • R 21 is a dihydric alcohol residue described later.
  • R 21 is preferably a divalent aliphatic hydrocarbon group.
  • R 22 is a divalent carboxylic acid residue described later.
  • R 22 includes a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group, and a divalent aliphatic hydrocarbon group is preferable.
  • R 23 is a residue derived from a cyclic ester or hydroxycarboxylic acid described later.
  • R 23 is preferably a divalent aliphatic hydrocarbon group.
  • the average molecular weight of one polyester chain is preferably 250 or more, more preferably 500 or more, and further preferably 1000 or more.
  • the polycarbonate chain is represented by, for example, —O—R 31 — (OC (O) OR 31 ) g — or — (OC (O) OR 31 ) g —.
  • R 31 is a divalent hydrocarbon group having 1 to 12 carbon atoms, and g is an integer of 2 or more.
  • R 31 may contain an aromatic hydrocarbon group, but is preferably a divalent aliphatic hydrocarbon group. Some hydrogen atoms may be substituted with fluorine or chlorine atoms.
  • the average molecular weight of one polycarbonate chain is preferably 250 or more, more preferably 500 or more, and further preferably 1000 or more.
  • the first linking group and the second linking group in the organic polymer skeleton are, for example, when a hydrolyzable silyl group is introduced at the end of a polyether polyol, polyester polyol or polycarbonate polyol in the production of a silyl group-containing polymer described later.
  • the group that is formed is, for example, when a hydrolyzable silyl group is introduced at the end of a polyether polyol, polyester polyol or polycarbonate polyol in the production of a silyl group-containing polymer described later.
  • the first linking group and the second linking group differ depending on the method of introducing a hydrolyzable silyl group at the end of the polyol.
  • Examples of the first linking group and the second linking group include — (O) p —R 13 —, — (O) p —C (O) NH—R 13 —, and the like.
  • R 13 is a divalent hydrocarbon group having 1 to 20 carbon atoms
  • p is 0 or 1
  • the R 13 side is bonded to the polysiloxane skeleton.
  • Some hydrogen atoms may be substituted with fluorine or chlorine atoms.
  • the chain linking group in the organic polymer skeleton is, for example, a group derived from a polyhydric alcohol that is an initiator in producing a polyether polyol, a polyester polyol, or a polycarbonate polyol described later.
  • the chain linking group is not particularly limited, and examples thereof include divalent to octavalent (preferably divalent to tetravalent, more preferably trivalent) organic groups, and typical examples thereof include the following groups.
  • the organic polymer skeleton may further have a terminal group composed of a hydrogen atom, a fluorine atom, a chlorine atom, and a monovalent organic group having a free terminal at the end, bonded to the polymer chain and not bonded to the polysiloxane skeleton. .
  • the polysiloxane skeleton is a skeleton in which siloxane bonds (Si—O—Si) are continuous.
  • the polysiloxane skeleton may have a pendant group bonded to Si. Examples of the pendant group include monovalent organic groups such as an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and those in which a hydrogen atom thereof is substituted with a halogen atom.
  • the polysiloxane wet gel includes a three-dimensional network structure and a solvent.
  • Solvents include water, alcohol (methanol, ethanol, isopropyl alcohol, tert-butyl alcohol, etc.), aprotic polar organic solvents (N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide, etc.), hydrocarbons (N-hexane, heptane, etc.), fluorine-containing solvents (2H, 3H-decafluoropentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, etc.), and mixtures thereof .
  • the polysiloxane xerogel is obtained by replacing the solvent contained in the wet gel with gas, and has a three-dimensional network structure.
  • the polysiloxane xerogel has a three-dimensional fine porous structure in which continuous pores exist between skeletons of a three-dimensional network structure.
  • the bending fracture strain of the polysiloxane gel is preferably 30% or more, more preferably 40% or more, and further preferably 50% or more. When the flexural fracture strain of the polysiloxane gel is 30% or more, the flexibility of the polysiloxane gel is sufficiently high.
  • the bending fracture strain of the polysiloxane gel is more preferably 150% or less, further preferably 100% or less, and particularly preferably 70% or less. If the bending fracture strain of the polysiloxane gel is 150% or less, the continuous pores in the polysiloxane xerogel are sufficiently formed, and the transparency and heat insulation of the polysiloxane xerogel are excellent.
  • the tensile fracture strain of the polysiloxane gel is preferably 1% or more, more preferably 5% or more, and further preferably 10% or more. If the tensile fracture strain of the polysiloxane gel is 1% or more, the polysiloxane gel is more difficult to tear.
  • the tensile fracture strain of the polysiloxane gel is preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less. When the tensile fracture strain of the polysiloxane gel is 50% or less, the continuous pores in the polysiloxane xerogel are sufficiently formed, and the transparency and heat insulation of the polysiloxane xerogel are excellent.
  • the 1 mm-thickness converted value of the light transmittance at a wavelength of 500 nm of the polysiloxane gel is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more.
  • the transmittance of the polysiloxane gel is 50% or more, the transparency of the polysiloxane gel is more excellent.
  • the thermal conductivity of the polysiloxane gel is preferably 5 mW / (m ⁇ K) or more, more preferably 10 mW / (m ⁇ K) or more, and further preferably 12 mW / (m ⁇ K) or more.
  • the thermal conductivity of the polysiloxane gel is 5 mW / (m ⁇ K) or more, the three-dimensional network structure is densely formed, and the bending fracture strain and the tensile fracture strain of the polysiloxane gel are increased.
  • the thermal conductivity of the polysiloxane gel is preferably 40 mW / (m ⁇ K) or less, more preferably 25 mW / (m ⁇ K) or less, and further preferably 20 mW / (m ⁇ K) or less.
  • the thermal conductivity of the polysiloxane gel is 40 mW / (m ⁇ K) or less, the heat insulation of the polysiloxane gel is more excellent.
  • the average pore diameter of the continuous pores in the polysiloxane xerogel is preferably 10 nm or more, more preferably 30 nm or more, and further preferably 40 nm or more. If the average pore diameter of the continuous pores is 10 nm or more, the heat insulating property of the polysiloxane xerogel is excellent.
  • the average pore diameter of continuous pores in the polysiloxane xerogel is preferably 150 nm or less, more preferably 100 nm or less, still more preferably 70 nm or less, and particularly preferably 50 nm or less.
  • the average pore diameter of the continuous pores is 150 nm or less, the heat insulation and transparency of the polysiloxane xerogel are excellent.
  • the average porosity of the polysiloxane xerogel is preferably 50% or more, more preferably 70% or more, and further preferably 80% or more. When the average porosity of the polysiloxane xerogel is 50% or more, the heat insulating property of the polysiloxane xerogel is excellent.
  • the average porosity of the polysiloxane xerogel is preferably 97% or less, more preferably 95% or less, still more preferably 93% or less, and particularly preferably 91% or less. When the average porosity of the polysiloxane xerogel is 97% or less, the bending fracture strain and tensile fracture strain of the polysiloxane xerogel increase.
  • the method for producing a polysiloxane gel of the present invention is a method having the following steps (i) to (iii).
  • the silyl group-containing polymer has a specific organic polymer skeleton and a hydrolyzable silyl group.
  • the organic polymer skeleton is the same as the organic polymer skeleton in the above-described three-dimensional network structure, and the preferred form is also the same.
  • the hydrolyzable silyl group becomes a silanol group (Si—OH) by a hydrolysis reaction during gelation, and further reacts between molecules to form a Si—O—Si bond to become a polysiloxane skeleton.
  • hydrolyzable silyl group examples include groups represented by the following formula (x). -SiR n L 3-n (x) Where R is a hydrogen atom or a monovalent hydrocarbon group, L is a hydrolyzable group, and n is an integer of 0-2.
  • R examples include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, and an alkyl group is preferable.
  • L examples include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, and the like. From the viewpoint of ease of production of the silyl group-containing polymer, a methoxy group or an ethoxy group is preferable, and from the viewpoint of good reactivity, A methoxy group is more preferred.
  • n is preferably 0 or 1 and more preferably 0 from the viewpoint of easily forming a three-dimensional network structure.
  • the silyl group-containing polymer preferably has at least two hydrolyzable silyl groups, and more preferably has at least three hydrolyzable silyl groups.
  • an organic polymer skeleton that is softer and tougher than the polysiloxane skeleton is incorporated in the middle of the path of the three-dimensional network structure, and the polysiloxane gel is bent and broken. Strain and tensile fracture strain are further increased.
  • the organic polymer skeleton becomes a branch point of the three-dimensional network structure, and the bending fracture strain and the tensile fracture strain of the polysiloxane gel are further increased.
  • Examples of the silyl group-containing polymer having a polyether chain include a polymer represented by the following formula. L 3-n R n Si—Q 12 — (OR 11 ) a —O—Q 11 —SiR n L 3-n G 1 [— (OR 11 ) a —OQ 11 —SiR n L 3-n ] b
  • O—Q 11 is a first linking group
  • Q 12 is a second linking group
  • G 1 is a chain linking group or a terminal group
  • b is an integer of 1 to 8. is there.
  • Q 11 and Q 12 examples include —R 13 —, —C (O) NH—R 13 —, and the like. However, the R 13 side is bonded to SiR n L 3-n . b is preferably an integer of 2 to 4, particularly preferably 3.
  • Examples of the silyl group-containing polymer having a polyester chain include a polymer represented by the following formula. L 3-n R n Si-Q 22 —O—R 21 — (OC (O) R 22 C (O) OR 21 ) c —O—Q 21 —SiR n L 3-n G 21 [— (OC (O) R 22 C (O) OR 21 ) c —OQ 21 —SiR n L 3-n ] d G 22 [— (OC (O) R 23 ) e —OQ 23 —SiR n L 3-n ] f
  • O-Q 21 and O-Q 23 are each a first linking group
  • Q 22 is a second linking group
  • G 21 and G 22 are each a chain linking group or a terminal group.
  • D and f are each an integer of 1 to 8.
  • Examples of Q 21 , Q 22 and Q 23 include —R 13 —, —C (O) NH—R 13 — and the like. However, the R 13 side is bonded to SiR n L 3-n . d and f are each preferably an integer of 2 to 4, particularly preferably 3.
  • Examples of the silyl group-containing polymer having a polycarbonate chain include a polymer represented by the following formula. L 3-n R n Si—Q 32 —O—R 31 — (OC (O) OR 31 ) g —O—Q 31 —SiR n L 3-n G 3 [— (OC (O) OR 31 ) g —OQ 31 —SiR n L 3-n ] h
  • O—Q 31 is a first linking group
  • Q 32 is a second linking group
  • G 3 is a chain linking group or a terminal group
  • h is an integer of 1 to 8. is there.
  • Examples of Q 31 and Q 32 include —R 13 —, —C (O) NH—R 13 —, and the like. However, the R 13 side is bonded to SiR n L 3-n . h is preferably an integer of 2 to 4, particularly preferably 3.
  • silyl group-containing polymer examples include Japanese Unexamined Patent Publication No. 6-340798, International Publication No. 2010/013653, International Publication No. 2010/041667, Japanese Unexamined Patent Publication No. 2010-111182, and Japanese Unexamined Patent Publication No. 2010-242070. And silyl group-containing polymers described in Japanese Patent No. 5447284.
  • Exastar manufactured by Asahi Glass Co., Ltd. modified polyether polymer having a hydrolyzable silyl group introduced at the end of a polyether polyol
  • the silyl group-containing polymer can be produced, for example, by the method described in Japanese Patent Application Laid-Open No. 6-340798, Japanese Patent No. 5447284, and the like. Specifically, a carbon-carbon unsaturated bond (vinyl group, allyl group, etc.) is introduced into the terminal hydroxyl group of polyether polyol, polyester polyol, polycarbonate polyol, or a polyol in which a plurality of polymer chains are combined, and carbon- Examples include a method of hydrosilylating a compound having a hydrosilyl group at a carbon unsaturated bond (HSiR n L 3-n ); a method of urethanating an isocyanate group-containing silane coupling agent to the hydroxyl group at the terminal of the polyol.
  • a carbon-carbon unsaturated bond (vinyl group, allyl group, etc.) is introduced into the terminal hydroxyl group of polyether polyol, polyester polyol, polycarbonate polyol, or
  • the polyether polyol can be produced by adding an alkylene oxide to a polyhydric alcohol that is an initiator.
  • the initiator include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, dextrose, sorbitol, sucrose and the like.
  • the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, epichlorohydrin and the like.
  • polyester polyol examples include a polyester polyol (1) having a polycarboxylic acid residue and a polyhydric alcohol residue, and a polyester polyol (2) having a ring-opening polymerization chain of a cyclic ester or a hydroxycarboxylic acid polymerization chain.
  • polyester polyol (1) there is a polyester polyol having a divalent carboxylic acid residue and a dihydric alcohol residue, and in some cases having a small amount of a trivalent or higher polyvalent carboxylic acid residue or polyhydric alcohol residue.
  • the polyvalent carboxylic acid include aliphatic dicarboxylic acids (such as adipic acid, sebacic acid, azelaic acid, and succinic acid), and aromatic dicarboxylic acids (such as phthalic acid, isophthalic acid, and terephthalic acid).
  • Polyhydric alcohols include diols (ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, etc.), trihydric or higher polyhydric alcohols (glycerin, trimethylolpropane, pentaerythritol, etc.) ) And the like.
  • polyester polyol (2) As the polyester polyol (2), a cyclic ester ( ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, etc.) or a hydroxycarboxylic acid (6-hydroxyhexanoic acid, etc.) is added to an initiator such as a polyhydric alcohol.
  • an initiator such as a polyhydric alcohol.
  • polyester polyols obtained polyester polyols obtained, and polyester polyols obtained by adding ⁇ -caprolactone to an initiator such as a polyhydric alcohol are preferred.
  • the initiator include the same initiators as used in the polyether polyol.
  • polycarbonate polyol examples include polyhexamethylene carbonate.
  • Examples of the solvent used in the step (i) include the solvents in the polysiloxane wet gel described above.
  • the solvent has good solubility and affinity with the silyl group-containing polymer, and forms a fine three-dimensional network structure to be transparent.
  • Alcohol is preferable from the viewpoint of easily obtaining a gel having excellent properties.
  • the mixture may further contain another silane compound having a hydrolyzable silyl group.
  • a skeleton derived from the other silane compound is introduced into the three-dimensional network structure, and the characteristics of the skeleton can be imparted to the polysiloxane gel.
  • the other silane compounds include alkoxysilanes; 6-membered ring-containing silane compounds having at least one 6-membered ring selected from the group consisting of an isocyanuric ring, a triazine ring, and a benzene ring, and a hydrolyzable silyl group. It is done.
  • Alkoxysilanes include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), monoalkyltrialkoxysilane (methyltrimethoxysilane, methyltriethoxysilane, etc.), dialkyl dialkoxysilane (dimethyldimethoxysilane, dimethyldiethoxysilane).
  • trimethoxyphenylsilane compounds having an alkoxysilyl group at both ends of the alkylene group (1,6-bis (trimethoxysilyl) hexane, 1,2-bis (trimethoxysilyl) ethane, etc.), perfluoropolyether Group-containing alkoxysilane (perfluoropolyether triethoxysilane, etc.), perfluoroalkyl group-containing alkoxysilane (perfluoroethyltriethoxysilane, etc.), pentafluorophenyl ether Sidimethylsilane, trimethoxy (3,3,3-trifluoropropyl) silane, alkoxysilane having a vinyl group (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), alkoxysilane having an epoxy group (2- (3,4) -Epoxycyclohexyl) ethyltrimethoxy
  • the 6-membered ring-containing silane compound includes, for example, a compound having a specific 6-membered ring and a carbon-carbon unsaturated bond (vinyl group, allyl group, etc.) (triallyl isocyanurate, divinylbenzene, trivinylbenzene, etc.), hydrosilyl A compound having a group (HSiR n L 3-n ) can be produced by a hydrosilylation reaction by a method described in Japanese Patent Application Laid-Open No. 2012-121852, Japanese Patent Application Laid-Open No. 2012-121853, or the like.
  • Examples of commercially available 6-membered ring-containing silane compounds include tris [3- (trimethoxysilyl) propyl] isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • the ratio of the silyl group-containing polymer in the total (100% by mass) of the silyl group-containing polymer and the other silane compound in the mixture is preferably 5 to 100% by mass, more preferably 20 to 100% by mass, and 50 to 100 mass% is more preferable.
  • the ratio of the silyl group-containing polymer is 5% by mass or more, the bending fracture strain and the tensile fracture strain of the polysiloxane gel are further increased.
  • silyl group-containing polymers and other silane compounds are hydrolyzed to generate silanol groups (Si—OH), which are then converted into molecular molecules. By reacting between them to form Si—O—Si bonds.
  • silyl group-containing polymer is a trifunctional polyether polyol having a methyldimethoxysilyl group introduced at the end thereof, two Si-O-Si are added to each of the two trimethoxysilyl groups as shown in the following formula. A bond is formed, and a three-dimensional network structure having an organic polymer skeleton and a polysiloxane skeleton is formed.
  • Examples of the base catalyst include amines (tetramethylammonium hydroxide, etc.), urea, ammonia, sodium hydroxide, potassium hydroxide and the like.
  • Examples of the acid catalyst include inorganic acids (such as nitric acid, sulfuric acid, and hydrochloric acid) and organic acids (such as formic acid, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid).
  • the mixture may further contain a surfactant such as hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride.
  • Step (ii) Solvent replacement is performed by immersing the wet gel in a solvent.
  • the solvent used in the step (ii) include the solvents in the above-described polysiloxane wet gel, and in the case of supercritical drying in the step (iii), it is preferable to substitute with alcohol such as methanol, ethanol, isopropyl alcohol, In the case of evaporating and drying in the step (iii), it is preferable to substitute with a hydrocarbon solvent such as hexane or heptane having a small surface tension, a fluorine-containing solvent (2H, 3H-decafluoropentane) or the like. In the case of freeze-drying in the step (iii), substitution with t-butanol, a fluorine-containing solvent (1,1,2,2,3,4,4-heptafluorocyclopentane) or the like is preferable.
  • Evaporative drying is performed, for example, by evaporating the solvent from the wet gel under conditions of a temperature of 30 to 100 ° C. and normal pressure.
  • Freeze-drying is performed, for example, by freezing the wet gel under the temperature of ⁇ 30 to 0 ° C. and then vacuum drying under the temperature of ⁇ 30 to 100 ° C.
  • Supercritical drying is performed, for example, by bringing supercritical carbon dioxide into contact with the wet gel under conditions of a temperature of 35 to 100 ° C. and a pressure of 7.4 to 30 MPa.
  • Mechanism of action In the method for producing the polysiloxane gel of the present invention described above, since it is a method of gelling a mixture containing a silyl group-containing polymer having a specific organic polymer skeleton and hydrolyzable silyl group and a solvent, A polysiloxane gel having a specific organic polymer skeleton and a polysiloxane skeleton and having a large bending fracture strain and tensile fracture strain can be produced.
  • the heat insulating material of the present invention includes the polysiloxane gel of the present invention.
  • the polysiloxane gel polysiloxane xerogel is preferable from the viewpoint of excellent heat insulation.
  • the heat insulating material of the present invention may be a sheet shape, a plate shape, or a molded body having an arbitrary shape.
  • the heat insulating material of the present invention may be composed of only a polysiloxane gel; may be a laminate composed of a layer composed of a polysiloxane gel and another layer; a sheet-like or plate-like polysiloxane A frame-like frame that supports the gel may be provided on the periphery.
  • other layers include an adhesive layer, a glass plate, a plastic plate, a plastic film, and a penetration-resistant film.
  • the heat insulating material of the present invention described above has a high heat insulating property because it is provided with a polysiloxane gel having heat insulating properties because fine pores are easily formed.
  • the polysiloxane gel of the present invention having a large bending fracture strain and tensile fracture strain is provided, the polysiloxane gel portion has flexibility and the polysiloxane gel portion is less likely to tear.
  • the laminated glass of the present invention is a transparent heat insulating layer made of the polysiloxane gel of the present invention, which exists between the first glass plate, the second glass plate, and the first glass plate and the second glass plate. With.
  • the laminated glass of the present invention may further have a transparent adhesive layer between the first glass plate or the second glass plate and the transparent heat insulating layer.
  • FIG. 1 is a cross-sectional view showing an example of the laminated glass of the present invention.
  • the laminated glass 1 includes: a first glass plate 10; a second glass plate 12; a transparent heat insulating layer 14 disposed between the first glass plate 10 and the second glass plate 12; A first transparent adhesive layer 16 for bonding the glass plate 10 and the transparent heat insulating layer 14; and a second transparent adhesive layer 18 for bonding the second glass plate 12 and the transparent heat insulating layer 14.
  • the material of the first glass plate and the second glass plate may be an inorganic glass or an organic glass, and has weather resistance, rigidity, and solvent resistance.
  • inorganic glass is preferable.
  • the materials of the first glass plate and the second glass plate may be the same or different.
  • the inorganic glass include soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Soda lime glass is preferable.
  • the organic glass include polycarbonate and acrylic resin.
  • the glass plate may be a colorless transparent glass plate or a colored transparent glass plate, and is preferably a heat ray absorbing glass plate (blue glass plate or green glass plate) rich in iron.
  • a tempered glass plate may be used to enhance safety.
  • a tempered glass plate obtained by an air cooling tempering method or a chemical tempering method can be used.
  • the shape of the glass plate may be curved or flat. Since the window glass for automobiles is often curved, when the laminated glass of the present invention is used as the window glass for automobiles, the shape of the glass plate is often curved.
  • the thickness of the glass plate is preferably 0.1 to 6 mm, more preferably 1 to 3 mm.
  • the thicknesses of the first glass plate and the second glass plate may be the same or different.
  • the thickness of the glass plate in this invention is geometric thickness. Hereinafter, the same applies to the thickness of each layer of the laminated glass of the present invention other than the glass plate.
  • the material of the first transparent adhesive layer and the second transparent adhesive layer may be any transparent resin that can adhere the glass plate and the transparent heat insulating layer.
  • the transparent resin include polyvinyl butyral, ethylene-vinyl acetate copolymer, and commercially available optically clear adhesive (OCA), and polyvinyl butyral and ethylene-vinyl acetate copolymer are preferable. Polyvinyl butyral is more preferable for applications requiring penetration resistance such as window glass.
  • the materials of the first transparent adhesive layer and the second transparent adhesive layer may be the same or different. Each transparent adhesive layer may be a laminate of two or more layers of the same or different types.
  • the transparent adhesive layer may contain an infrared absorber, an ultraviolet absorber, an antioxidant, a light stabilizer, a colorant and the like within a range not impairing the effects of the present invention.
  • the thickness of the transparent adhesive layer is preferably from 0.1 to 3 mm, and more preferably from 0.3 to 0.8 mm.
  • the thickness of the first transparent adhesive layer and the second transparent adhesive layer may be the same or different.
  • a transparent heat insulation layer consists of a sheet-like polysiloxane gel of the present invention.
  • polysiloxane gel polysiloxane xerogel is preferable from the viewpoint of excellent heat insulation.
  • the compression elastic modulus of the transparent heat insulation layer is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, and further preferably 1 MPa or more. When the compression elastic modulus is 0.1 MPa or more, the transparent heat insulating layer is excellent in mechanical strength and can withstand compression when laminated with a glass plate during the production of laminated glass.
  • the thickness of the transparent heat insulating layer is preferably 0.2 to 10 mm, more preferably 0.5 to 6 mm, and further preferably 1 to 3 mm. If the thickness of a transparent heat insulation layer is more than the lower limit of the said range, it will be further excellent in the heat insulation of laminated glass. If the thickness of a transparent heat insulation layer is below the upper limit of the said range, the transparency of a laminated glass will become still higher.
  • the transmittance of light having a wavelength of 500 nm of the laminated glass is preferably 50% or more, more preferably 70 to 99%, and further preferably 70 to 96%. If the transmittance
  • the thermal penetration rate (U value) of laminated glass is 5.8 W / m 2 K in the current laminated glass for automobiles, and is preferably 5.0 W / m 2 K or less from the viewpoint of improving fuel efficiency. More preferable is 0.0 W / m 2 K or less.
  • the thickness of the laminated glass is preferably 2 to 20 mm, more preferably 3 to 10 mm, and even more preferably 4 to 6 mm. If the thickness of the laminated glass is not less than the lower limit of the above range, the heat insulating property of the laminated glass is further improved, and the mechanical strength is also excellent. If the thickness of a laminated glass is below the upper limit of the said range, a laminated glass will not become too heavy and it is excellent also in transparency.
  • Laminated glass can be produced by a known method.
  • the second glass plate, the transparent resin sheet serving as the second transparent adhesive layer, the sheet-like polysiloxane gel of the present invention serving as the transparent heat insulating layer, the transparent resin sheet serving as the first transparent adhesive layer, the first It can manufacture by carrying out this adhesion
  • the transparent resin sheet serving as the first transparent adhesive layer and the transparent resin sheet serving as the second transparent adhesive layer may each be the same type or may be composed of two or more different types of sheets. Good.
  • the laminated glass of the present invention is a transparent heat insulating layer made of the polysiloxane gel of the present invention, which exists between the first glass plate, the second glass plate, and the first glass plate and the second glass plate. And is not limited to the illustrated example.
  • the laminated glass of this invention may have a 3rd glass plate or more glass plates as needed.
  • the laminated glass of this invention may have functional layers other than a transparent heat insulation layer, such as an infrared absorption layer and an ultraviolet absorption layer.
  • the laminated glass of the present invention described above has a high heat insulating property because it includes a transparent heat insulating layer made of polysiloxane gel. Further, since the transparent heat insulating layer is the polysiloxane gel of the present invention having a large bending fracture strain and tensile fracture strain, the transparent heat insulating layer has flexibility and the transparent heat insulating layer is hardly broken.
  • the average pore diameter of the continuous pores in xerogel is 50% higher than the integrated pore volume plot of the BJH method adsorption by measuring the nitrogen adsorption method using a pore distribution measuring device (manufactured by Shimadzu Corporation, 3Flex-2MP). This is a value of a pore diameter generally called a median diameter.
  • the bending fracture strain of polysiloxane xerogel is based on JIS K 7171: 2008 (ISO 178: 2001), and is a single type gel using a desktop precision universal testing machine (manufactured by Shimadzu Corporation, Autograph AGS-5kNX). Three samples of each were measured, and the arithmetic average value was obtained.
  • the tensile fracture strain of polysiloxane xerogel is based on JIS K 7161: 1994 (ISO 5271: 1993), and is a single type of gel using a desktop precision universal testing machine (manufactured by Shimadzu Corporation, Autograph AGS-5kNX). Three samples of each were measured, and the arithmetic average value was obtained.
  • the transmittance of light having a wavelength of 500 nm of the polysiloxane xerogel was measured using a spectrophotometer (manufactured by Shimadzu Corporation, SolidSpec-3700DUV) in accordance with JIS R 3106: 1998 (ISO 9050: 1990).
  • Thermal conductivity of the polysiloxane xerogel was measured according to JIS A 1412-2: 1999 (ISO 8301: 1991) by using a thermal conductivity measuring device (HC-074 / 630, manufactured by Eiko Seiki Co., Ltd.).
  • the compression modulus of polysiloxane xerogel is based on JIS K 7181: 2011 (ISO 604: 2002), and using a tabletop precision universal testing machine (manufactured by Shimadzu Corporation, Autograph AGS-5kNX) Three samples of each were measured and the arithmetic average value was obtained.
  • Example 1 5 g of the silyl group-containing polymer (A) and 30 g of methanol were placed in a plastic container containing a magnetic stirrer and stirred at room temperature for 1 minute. To this was added 2 g of a 0.75 mol / L tetramethylammonium hydroxide aqueous solution as a base catalyst and surfactant, and the mixture was stirred at 1500 rpm for 10 seconds to obtain a mixture. The resulting mixture was placed in two polypropylene trays with varying thicknesses of each liquid. Thereafter, the tray was placed in a stainless steel sealed container, the lid was closed, and the sealed tray was placed in a 60 ° C. oven to proceed with gelation.
  • the container was taken out of the oven, and the methanol gel in the tray was immersed in hexane in another stainless steel sealed container. Every 24 hours, the hexane in the container was replaced with new hexane. The exchange of hexane was repeated 4 times to obtain a hexane gel.
  • the obtained hexane gel was placed in an oven at 60 ° C. and dried at atmospheric pressure for 24 hours to obtain polysiloxane xerogels having a thickness of 1 mm and 10 mm. The transmittance of the obtained polysiloxane xerogel having a thickness of 1 mm was measured.
  • the resulting polysiloxane xerogel having a thickness of 10 mm had an average pore diameter, average porosity, bending fracture strain, tensile fracture strain, thermal conductivity, and compression elasticity. The rate was measured. The results are shown in Table 1.
  • Example 2 Carbon dioxide supercritical drying was performed using methanol gel obtained by the same method as in Example 1 to obtain polysiloxane xerogel. Specifically, the high-pressure vessel was filled with methanol, and methanol gel was put therein. After making a closed system with a lid, liquefied carbon dioxide gas was introduced at 20 ° C. at a rate of 10 mL / min, and adjusted and maintained with a back pressure valve so that the pressure was constant at 26 MPa. After this operation was continued for 24 hours, the temperature of the high-pressure vessel was raised to 50 ° C. while maintaining the pressure at 26 MPa, thereby obtaining a supercritical state. Thereafter, carbon dioxide was kept flowing at 5 mL / min to maintain 26 MPa.
  • Example 3 A tert-butyl alcohol gel was obtained in the same manner as in Example 1 except that tert-butyl alcohol was used instead of methanol.
  • the obtained tert-butyl alcohol gel was frozen in a freezer at ⁇ 30 ° C. for 16 hours, then placed in a vacuum dryer and freeze-dried at 0 ° C. for 2 days to obtain a polysiloxane xerogel having a thickness of 1 mm and 10 mm. Got.
  • the same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 1.
  • Example 4 Place 3 g of silyl group-containing polymer (A), 2 g of isocyanuric acid tris [3- (trimethoxysilyl) propyl] (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 30 g of ethanol, and put in a plastic container containing a magnetic stir bar. And stirred for 1 minute. To this was added 2 g of a 0.75 mol / L tetramethylammonium hydroxide aqueous solution as a base catalyst and surfactant, and the mixture was stirred at 1500 rpm for 10 seconds to obtain a mixture.
  • a polysiloxane xerogel having a thickness of 1 mm and 10 mm was obtained in the same manner as in Example 1 except that this mixture was used. The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 2.
  • Example 5 Instead of using 3 g of silyl group-containing polymer (A), 2 g of tris [3- (trimethoxysilyl) propyl] isocyanurate and 30 g of ethanol, 1 g of silyl group-containing polymer (A) and methyltrimethoxysilane (Tokyo Kasei) A polysiloxane xerogel having a thickness of 1 mm and 10 mm was obtained in the same manner as in Example 4 except that 4 g of Kogyo Co., Ltd. and 30 g of N, N-dimethylformamide (hereinafter also referred to as DMF) were used. The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 2.
  • Example 6 A polysiloxane xerogel having a thickness of 1 mm and 10 mm was obtained in the same manner as in Example 4 except that 2 g of methyltrimethoxysilane was used instead of 2 g of tris [3- (trimethoxysilyl) propyl] isocyanurate. . The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 2.
  • the polysiloxane gel of the present invention is useful as a heat insulating material, a transparent heat insulating layer of laminated glass, and the like.
  • the laminated glass of the present invention includes automotive window glass (windshield, roof window, elevating window, side fixing window, backlight, roof window, etc.), vehicle window glass such as railcar window glass, and building window glass. Useful as such.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

L'invention a pour objet de fournir un gel de polysiloxane présentant un important effort de rupture à la flexion et à la traction. Plus précisément, l'invention concerne un gel de polysiloxane qui contient une structure en réseau tridimensionnel possédant : un squelette de polymère organique qui possède au moins une sorte de chaîne polymère choisie dans un groupe constitué d'une chaîne polyéther, d'une chaîne polyester et d'une chaîne polycarbonate ; et un squelette de polysiloxane.
PCT/JP2017/041702 2016-11-24 2017-11-20 Gel de polysiloxane ainsi que procédé de fabrication de celui-ci, matériau d'isolation thermique, et verre feuilleté WO2018097106A1 (fr)

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WO2019039541A1 (fr) * 2017-08-25 2019-02-28 国立大学法人京都大学 Gel de faible densité et son procédé de production
JP2021134105A (ja) * 2020-02-26 2021-09-13 Ａｇｃ株式会社 多孔体の製造方法
WO2022045027A1 (fr) * 2020-08-26 2022-03-03 Ａｇｃ株式会社 Structure de plaque en verre, diaphragme et élément d'ouverture

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JPH03162414A (ja) * 1989-11-06 1991-07-12 Union Carbide Chem & Plast Co Inc シリコーンポリエーテル共重合体表面活性剤
JP2006036888A (ja) * 2004-07-26 2006-02-09 Sekisui Chem Co Ltd 加水分解性官能基を有するポリマーの架橋ポリマーの製造方法及び加水分解性官能基を有するポリマーの架橋ポリマー
WO2016094778A1 (fr) * 2014-12-12 2016-06-16 Exxonmobil Research And Engineering Company Matériaux organosiliciés et leurs utilisations

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JPH03162414A (ja) * 1989-11-06 1991-07-12 Union Carbide Chem & Plast Co Inc シリコーンポリエーテル共重合体表面活性剤
JP2006036888A (ja) * 2004-07-26 2006-02-09 Sekisui Chem Co Ltd 加水分解性官能基を有するポリマーの架橋ポリマーの製造方法及び加水分解性官能基を有するポリマーの架橋ポリマー
WO2016094778A1 (fr) * 2014-12-12 2016-06-16 Exxonmobil Research And Engineering Company Matériaux organosiliciés et leurs utilisations

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019039541A1 (fr) * 2017-08-25 2019-02-28 国立大学法人京都大学 Gel de faible densité et son procédé de production
US11518855B2 (en) 2017-08-25 2022-12-06 Kyoto University Low-density gel product and production method therefor
JP2021134105A (ja) * 2020-02-26 2021-09-13 Ａｇｃ株式会社 多孔体の製造方法
JP7426852B2 (ja) 2020-02-26 2024-02-02 Ａｇｃ株式会社 多孔体の製造方法
WO2022045027A1 (fr) * 2020-08-26 2022-03-03 Ａｇｃ株式会社 Structure de plaque en verre, diaphragme et élément d'ouverture

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