WO2018097103A1

WO2018097103A1 - Polysiloxane gel, method for producing same, thermal insulating material, and laminated glass

Info

Publication number: WO2018097103A1
Application number: PCT/JP2017/041687
Authority: WO
Inventors: 室伏　英伸; 千恵子室伏
Original assignee: 旭硝子株式会社
Priority date: 2016-11-24
Filing date: 2017-11-20
Publication date: 2018-05-31
Also published as: JP2020015773A

Abstract

The purpose of this invention is to provide a polysiloxane gel having a high bend fracture stress. This invention pertains to a polysiloxane gel including a three-dimensional network structure including a polysiloxane core and a six-membered ring-containing core having at least one type of six-membered ring selected from the group consisting of a ring structure represented by formula (a), a ring structure represented by formula (b) and a ring structure represented by formula (c). In formulae (a) to (c), * represents a bond.

Description

Polysiloxane gel, production method thereof, heat insulating material and laminated glass

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.

As the transparent heat insulating material, for example, 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).

International Publication No. 2007/010949

However, 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.

The present invention relates to a polysiloxane gel having a high bending fracture stress; a method capable of producing a polysiloxane gel having a high bending fracture stress; a heat insulating material having a high heat insulating property and being less prone to cracking; and a high heat insulating property and a transparent heat insulating layer. To provide a laminated glass which is not easily broken.

The polysiloxane gel of the present invention is at least selected from the group consisting of a ring structure represented by the following formula (a), a ring structure represented by the following formula (b), and a ring structure represented by the following formula (c). A three-dimensional network structure having a six-membered ring-containing skeleton having one kind of six-membered ring and a polysiloxane skeleton is included.

However, * in the formulas (a) to (c) is a bond.
The method for producing a polysiloxane gel of the present invention comprises a ring structure represented by the following formula (a), a ring structure represented by the following formula (b), and a ring structure represented by the following formula (c). A method for producing a polysiloxane gel comprising a three-dimensional network structure having a six-membered ring-containing skeleton having at least one selected six-membered ring and a polysiloxane skeleton; a ring represented by the following formula (a) A 6-membered ring-containing skeleton having at least one 6-membered ring selected from the group consisting of a structure, a ring structure represented by the following formula (b), and a ring structure represented by the following formula (c); A 6-membered ring-containing silane compound having a group and a solvent are gelled to obtain a wet gel.

However, * in the formulas (a) to (c) is a bond.
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 high bending fracture stress.
According to the method for producing a polysiloxane gel of the present invention, a polysiloxane gel having a high bending fracture stress can be produced.
The heat insulating material of the present invention has high heat insulating properties and is not easily cracked.
The laminated glass of the present invention has high heat insulating properties and is less likely to crack in the transparent heat insulating layer.

FIG. 1 is a cross-sectional view showing an example of the laminated glass of the present invention.

The following term definitions apply throughout this specification and the claims.
The “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." There is also a classification method in which 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, and 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.
“Bending fracture stress” is a value measured in accordance with JIS K 7171: 2008 “Plastics—How to obtain bending characteristics” (ISO 178: 2001).
“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 “average porosity” is a value obtained from the following equation from the volume of xerogel before pressing and the volume of xerogel after pressing under conditions of temperature: 100 ° C., pressure: 50 MPa, time: 10 minutes.
Average porosity = {1− (volume of xerogel after pressing / volume of xerogel before pressing)} × 100
The “compressive modulus” is a value measured in accordance with JIS K 7181: 2011 “Plastics—How to obtain compression properties” (ISO 604: 2002).

<Polysiloxane gel>
The polysiloxane gel of the present invention includes a three-dimensional network structure having a specific six-membered ring-containing 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.

(Six-membered ring-containing skeleton)
The 6-membered ring-containing skeleton has a specific 6-membered ring.
The 6-membered ring-containing skeleton preferably further has a linking group interposed between the 6-membered ring and the polysiloxane skeleton.

The 6-membered ring-containing skeleton has a plurality of bonds, and at least two of the plurality of bonds are preferably bonded directly or indirectly to the polysiloxane skeleton. It is more preferable that at least three of the bonds are directly or indirectly bonded to the polysiloxane skeleton. The two bond hands of the 6-membered ring-containing skeleton are directly or indirectly bonded to the polysiloxane skeleton, so that the 6-membered ring-containing skeleton is incorporated in the course of the three-dimensional network structure, and the bending fracture stress of the polysiloxane gel Is even higher. Since the three bonds of the 6-membered ring-containing skeleton are directly or indirectly bonded to the polysiloxane skeleton, the 6-membered ring-containing skeleton becomes a branch point of the three-dimensional network structure, and the bending fracture stress of the polysiloxane gel is further increased. Become.

(6-member ring)
The 6-membered ring in the 6-membered ring-containing skeleton includes a ring structure represented by the following formula (a) (hereinafter also referred to as ring structure (a)) and a ring structure represented by the following formula (b) (hereinafter referred to as ring). And at least one selected from the group consisting of a ring structure represented by the following formula (c) (hereinafter also referred to as ring structure (c)).

However, * in the formulas (a) to (c) is a bond. In the ring structure (a) and the ring structure (b), it is preferable that two or three of three bonds are directly or indirectly bonded to the polysiloxane skeleton, and three are directly or indirectly bonded to the polysiloxane skeleton. More preferably, it binds to. In the ring structure (c), it is preferable that 2 to 4 of the 6 bonds are directly or indirectly bonded to the polysiloxane skeleton, and 3 or 4 are directly or indirectly bonded to the polysiloxane skeleton. Is more preferable. Of the bonds in each ring structure, bonds not directly or indirectly bonded to the polysiloxane skeleton are bonded to, for example, other groups described later.
The 6-membered ring-containing skeleton may have multiple types of 6-membered rings.
As the 6-membered ring, the ring structure (a) is preferable from the viewpoint of easy availability of the 6-membered ring-containing silane compound as a raw material.

(Linking group)
The linking group in the 6-membered ring-containing skeleton is, for example, a group formed when a hydrolyzable silyl group is introduced into the 6-membered ring in the production of the 6-membered ring-containing silane compound described later.
When the 6-membered ring-containing skeleton has a linking group, the proportion of the 6-membered ring-containing skeleton that is an organic skeleton in the three-dimensional network structure is increased, and the bending fracture stress of the polysiloxane gel is further increased.

The linking group is a divalent or higher valent group having at least one group selected from the group consisting of an alkylene group, an oxyalkylene group, a polyether chain, and an arylene group. As the linking group, a divalent group having an alkylene group, a polyether chain or an oxyalkylene group is preferable from the viewpoint of easy availability of the 6-membered ring-containing silane compound as a raw material, and a divalent group having an alkylene group. Groups are more preferred.
The alkylene group preferably has 1 to 18 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 6 carbon atoms. When the number of carbon atoms of the alkylene group is not less than the lower limit of the above range, the bending fracture stress of the polysiloxane gel is further increased. When the number of carbon atoms of the alkylene group is not more than the upper limit of the above range, shrinkage during gel drying can be reduced and the porosity can be prevented from being reduced.

The linking group may further have a bond such as —O—, —NH—, —C (O) O—, —NHC (O) — or the like at the terminal or in the middle.

(Other groups)
The 6-membered ring-containing skeleton may further have a hydrogen atom, a fluorine atom, a chlorine atom, or a monovalent organic group having a free end at the end, bonded to the 6-membered ring and not bonded to the polysiloxane skeleton.

(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.

(Polysiloxane wet gel)
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 .

(Polysiloxane xerogel)
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.

(Bending fracture stress)
The bending fracture stress of the polysiloxane gel is preferably 0.3 MPa or more, more preferably 0.5 MPa or more, further preferably 1 MPa or more, particularly preferably 3 MPa or more, and most preferably 6 MPa or more. When the bending fracture stress of the polysiloxane gel is 0.3 MPa or more, the polysiloxane gel does not become brittle and the usability is better. The bending fracture stress of the polysiloxane gel is preferably 50 MPa or less, more preferably 30 MPa or less, further preferably 20 MPa or less, particularly preferably 15 MPa or less, and most preferably 10 MPa or less. If the bending fracture stress of the polysiloxane gel is 50 MPa or less, continuous pores in the polysiloxane xerogel are sufficiently formed, and the heat insulation of the polysiloxane xerogel is excellent.

(Transmittance)
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 further preferably 80% or more. If the transmittance of the polysiloxane gel is not less than the lower limit of the above range, the transparency of the polysiloxane gel is excellent. The higher the 1 mm-thickness converted value of the transmittance of light having a wavelength of 500 nm of the polysiloxane gel, the better, and the upper limit is 100%.

(Thermal conductivity)
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. When 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 stress of the polysiloxane gel is 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. When the thermal conductivity of the polysiloxane gel is 40 mW / (m · K) or less, the heat insulation of the polysiloxane gel is more excellent.

(Pore size and porosity)
It is possible to achieve both transparency and heat insulation of the polysiloxane gel by adjusting the pore diameter and porosity of the continuous pores in the polysiloxane xerogel.
The average pore diameter of continuous pores in the polysiloxane xerogel is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 40 nm or more, and particularly preferably 50 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 60 nm or less. When 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, still more preferably 80% or more, and particularly preferably 90% 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, and further preferably 93% or less. When the average porosity of the polysiloxane xerogel is 97% or less, the bending fracture stress of the polysiloxane xerogel increases.

(Mechanism of action)
In the polysiloxane gel of the present invention described above, the bending fracture stress is high due to the composite of the specific six-membered ring-containing skeleton that is an organic skeleton and the polysiloxane skeleton that is an inorganic skeleton.

<Method for producing polysiloxane gel>
The method for producing a polysiloxane gel of the present invention is a method having the following steps (i) to (iii).
Step (i): A step of gelling a mixture containing a specific 6-membered ring-containing silane compound and a solvent to obtain a wet gel.
Step (ii): A step of replacing the solvent of the wet gel as necessary.
Step (iii): A step of removing the solvent from the wet gel as necessary to obtain a xerogel.

(6-membered ring-containing silane compound)
The 6-membered ring-containing silane compound has a specific 6-membered ring-containing skeleton and a hydrolyzable silyl group.
The six-membered ring-containing skeleton is the same as the six-membered ring-containing 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.

Examples of the hydrolyzable silyl group 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.

Examples of R include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, and an alkyl group is preferable.
Examples of L include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, and the like. From the viewpoint of easy production of a 6-membered ring-containing silane compound, a methoxy group or an ethoxy group is preferable, and the reactivity is excellent. Therefore, a methoxy group is more preferable.
n is preferably 0 or 1 and more preferably 0 from the viewpoint of easily forming a three-dimensional network structure.

The 6-membered ring-containing silane compound preferably has at least two hydrolyzable silyl groups, and more preferably has at least three hydrolyzable silyl groups. When the 6-membered ring-containing silane compound has at least two hydrolyzable silyl groups, the 6-membered ring-containing skeleton is incorporated in the course of the three-dimensional network structure, and the bending fracture stress of the polysiloxane gel is further increased. When the 6-membered ring-containing silane compound has at least three hydrolyzable silyl groups, the 6-membered ring-containing skeleton becomes a branch point of the three-dimensional network structure, and the bending fracture stress of the polysiloxane gel is further increased.

Examples of the 6-membered ring-containing silane compound include a compound having a ring structure (a) and a hydrolyzable silyl group (hereinafter also referred to as compound (α)), a ring structure (b) and a hydrolyzable silyl group. And a compound having a ring structure (c) and a hydrolyzable silyl group (hereinafter also referred to as compound (γ)), and the like.

Preferred examples of the compound (α) include, for example, a compound represented by the following formula (α1). Preferable examples of the compound (β) include a compound represented by the following formula (β1). Preferable examples of the compound (γ) include a compound represented by the following formula (γ1).

However, Q ¹ , Q ² and Q ³ are each a linking group. p is an integer of 1 to 3, and 2 or 3 is preferable. In the ring structure (c) of the formula (γ1), other groups (hydrogen atom, fluorine atom, chlorine atom, monovalent organic group) described above are bonded to carbon atoms other than the carbon atom to which Q ³ is bonded. The plurality of Q ¹ may be the same group or may be partially or entirely different groups. The same applies to Q ² , Q ³ and SiR _n L _3-n . R is a hydrogen atom or a monovalent hydrocarbon group, L is a hydrolyzable group, and n is an integer of 0-2.

Examples of Q ¹ , Q ^2, and Q ³ include a divalent or higher valent group having at least one group selected from the group consisting of an alkylene group, an oxyalkylene group, a polyether chain, and an arylene group. Q ¹ , Q ² and Q ³ are each preferably — (CH ₂ ) _m — or —O (CH ₂ ) _m — (where m is an integer of 1 to 18).

The compound (α) is preferably a compound (α1-1) represented by the following formula from the viewpoint of availability. The compound (α1-1) can be obtained from Tokyo Chemical Industry Co., Ltd.

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.

(Process (i))
Examples of the solvent used in the step (i) include the solvents in the polysiloxane wet gel described above. The compound (α) has good solubility and affinity with the gel, and forms a fine three-dimensional network structure to be transparent. An aprotic polar organic solvent or an alcohol is preferable from the viewpoint that a gel having excellent properties can be easily obtained. Moreover, it is preferable that the water for hydrolysis of a hydrolysable silyl group is included.

The mixture may further contain another silane compound having a hydrolyzable silyl group. When the mixture further contains another silane compound, 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.
Examples of other silane compounds include alkoxysilanes; silyl group-containing polymers having an organic polymer skeleton having at least one chain selected from the group consisting of polyether chains, polyester chains, and polycarbonate chains, and hydrolyzable silyl groups. Can be mentioned.

Alkoxysilanes include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), monoalkyltrialkoxysilane (methyltrimethoxysilane, methyltriethoxysilane, etc.), dialkyl dialkoxysilane (dimethyldimethoxysilane, dimethyldiethoxysilane). Etc.), 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) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.), alkoxysilane having an acryloyloxy group ( 3-acryloyloxypropyltrimethoxysilane and the like.

Examples of the silyl group-containing polymer 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.
As a commercial product of a silyl group-containing polymer, Exastar manufactured by Asahi Glass Co., Ltd. (modified polyether polymer having a hydrolyzable silyl group introduced at the end of a polyether polyol) and the like can be mentioned.

The ratio of the 6-membered ring-containing silane compound to the total (100 mass%) of the 6-membered ring-containing silane compound and other silane compounds in the mixture is preferably 5 to 100 mass%, more preferably 20 to 100 mass%. 50 to 100% by mass is more preferable. If the ratio of the 6-membered ring-containing silane compound is not less than the lower limit of the above range, the bending fracture stress of the polysiloxane gel will be further increased.

In the gelation of the mixture, in the presence of a base catalyst or an acid catalyst, hydrolyzable silyl groups of 6-membered ring-containing silane compounds and other silane compounds are hydrolyzed to form silanol groups (Si—OH). Is caused to react between molecules to form a Si—O—Si bond. For example, when the 6-membered ring-containing silane compound is a compound represented by the formula (α1-1), three Si—O—Si bonds are formed in each of three trimethoxysilyl groups as shown in the following formula. A three-dimensional network structure having a 6-membered ring-containing 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.
Examples of 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, When evaporating and drying in the step (iii), it is preferable to substitute a hydrocarbon solvent such as hexane or heptane having a low surface tension or a fluorine-containing solvent (2H, 3H-decafluoropentane), etc., and freezing in the step (iii). In the case of drying, substitution with t-butanol or a fluorine-containing solvent (1,1,2,2,3,3,4-heptafluorocyclopentane) or the like is preferable.

(Process (iii))
Known methods for drying wet gels include atmospheric drying, freeze drying (freeze drying), subcritical drying, and supercritical drying.

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, a method of gelling a mixture containing a 6-membered ring-containing silane compound having a specific 6-membered ring-containing skeleton and a hydrolyzable silyl group and a solvent. Therefore, a polysiloxane gel having a specific 6-membered ring-containing skeleton that is an organic skeleton and a polysiloxane skeleton that is an inorganic skeleton can be produced.

<Insulation material>
The heat insulating material of the present invention includes the polysiloxane gel of the present invention. As 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.
Examples of other layers include an adhesive layer, a glass plate, a plastic plate, a plastic film, and a penetration-resistant film.

Since the heat insulating material of the present invention described above is provided with a polysiloxane gel having heat insulating properties, the heat insulating properties are high. Moreover, since the polysiloxane gel of the present invention having a high bending fracture stress is provided, cracks are unlikely to occur in the polysiloxane gel portion.

<Laminated glass>
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.

(Glass plate)
The material of the first glass plate and the second glass plate (hereinafter collectively referred to as a glass plate) may be an inorganic glass or an organic glass, and has weather resistance, rigidity, and solvent resistance. In view of the above, inorganic glass is preferable. The materials of the first glass plate and the second glass plate may be the same or different.
Examples of the inorganic glass include soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Soda lime glass is preferable.
Examples of 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.
As the glass plate, a tempered glass plate may be used to enhance safety. As the tempered glass plate, 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. In addition, 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.

(Transparent adhesive layer)
The material of the first transparent adhesive layer and the second transparent adhesive layer (hereinafter collectively referred to as a transparent adhesive layer) may be any transparent resin that can adhere the glass plate and the transparent heat insulating layer. Examples of 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.

(Transparent insulation layer)
A transparent heat insulation layer consists of a sheet-like polysiloxane gel of the present invention. As the polysiloxane gel, polysiloxane xerogel is preferable from the viewpoint of excellent heat insulation.
The compression elastic modulus of the transparent heat insulating layer is preferably 1.3 MPa or more, more preferably 4.3 MPa or more, further preferably 5.0 MPa or more, and particularly preferably 12 MPa or more. When the compression elastic modulus is 1.0 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 a 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.

(Characteristics of laminated glass)
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 80 to 96%. If the transmittance | permeability of the light of wavelength 500nm is more than the lower limit of the said range, the transparency of a laminated glass will become high. It is difficult to produce a laminated glass having a light transmittance of a wavelength of 500 nm exceeding the upper limit of the above range.

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 manufacturing method)
Laminated glass can be produced by a known method. For example, 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 | attachment by superposing | stacking a glass plate in order and carrying out temporary adhesion | attachment of these, and heating and pressurizing. At this time, 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.

(Other forms)
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.

For 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.

(Mechanism of action)
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. Moreover, since a transparent heat insulation layer is the polysiloxane gel of this invention with a high bending fracture stress, it is hard to produce a crack in a transparent heat insulation layer.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Average pore size)
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.

(Average porosity)
The average porosity of the xerogel was determined by the following equation from the volume of the xerogel before pressing and the volume of the xerogel after pressing under the conditions of temperature: 100 ° C., pressure: 50 MPa, time: 10 minutes.
Average porosity = {1− (volume of xerogel after pressing / volume of xerogel before pressing)} × 100

(Bending fracture stress)
The bending fracture stress of polysiloxane xerogel is based on JIS K 7171: 2008 (ISO 178: 2001), and is a single 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.

(Transmittance)
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)
The 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.).

(Compressive modulus)
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 compound (α1-1) (manufactured by Tokyo Chemical Industry Co., Ltd., isocyanuric acid tris [3- (trimethoxysilyl) propyl]) and 30 g of N, N-dimethylformamide (hereinafter also referred to as DMF), a magnetic stirring bar Was placed in a plastic container containing, 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 obtained mixture was placed in two polypropylene trays with different liquid thicknesses. Thereafter, the tray was placed in a stainless steel sealed container, the lid was closed, and the sealed container was placed in an oven at 60 ° C. for gelation. Three days later, the container was taken out from the oven, and the wet gel in the tray was immersed in methanol in another sealed stainless steel container. Every 24 hours, the methanol in the container was replaced with new methanol. Methanol exchange was repeated 4 times to obtain a methanol gel. The solvent was replaced with hexane, and the same solvent replacement was repeated four times to replace the methanol gel solvent with hexane, thereby obtaining a hexane gel. The obtained hexane gel was put into 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 was measured for the obtained polysiloxane xerogel having a thickness of 1 mm, and the average pore diameter, average porosity, bending fracture stress, thermal conductivity, and compression modulus were measured for the obtained polysiloxane xerogel having a thickness of 10 mm. . 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, methanol was filled in a high-pressure vessel, 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. After 3 hours, supercritical carbon dioxide was purged and returned to normal pressure over 1 hour. Thereafter, the high-pressure vessel was opened, the xerogel was taken out, and dried in a vacuum oven at 50 ° C. for 16 hours to obtain polysiloxane xerogel having a thickness of 1 mm and 10 mm. The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 1.

(Example 3)
Polysiloxane xerogels having a thickness of 1 mm and 10 mm were obtained in the same manner as in Example 1 except that dimethyl sulfoxide (hereinafter also referred to as DMSO) was used instead of DMF. The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 1.

Example 4
A thickness of 1 mm was obtained in the same manner as in Example 1 except that 3 g of compound (α1-1) and 2 g of methyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of 5 g of compound (α1-1) And 10 mm polysiloxane xerogel was obtained. 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 5 g of the compound (α1-1), a polysiloxane xerogel having a thickness of 1 mm and 10 mm was prepared in the same manner as in Example 1 except that 1 g of the compound (α1-1) and 4 g of methyltrimethoxysilane were used. Obtained. The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 2.

(Example 6)
0.5 g of compound (α1-1), 4.5 g of methyltrimethoxysilane, 30 g of 5 mmol / L acetic acid aqueous solution as a solvent, 2 g of urea as a base catalyst, and hexadecyltrimethylammonium bromide as a surfactant ( 0.75 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a plastic container containing a magnetic stirrer and stirred at room temperature for 60 minutes at a rotation speed of 1500 rpm 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 7)
Instead of using 5 g of the compound (α1-1), a thickness of 1 mm was obtained in the same manner as in Example 1 except that 1 g of the compound (α1-1) and 4 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were used. A 10 mm polysiloxane xerogel was obtained. The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 3.

(Example 8)
Instead of using 5 g of compound (α1-1), 2.5 g of compound (α1-1) and 2.5 g of 1,6-bis (trimethoxysilyl) hexane (manufactured by Tokyo Chemical Industry Co., Ltd.) were used. Polysiloxane xerogels having a thickness of 1 mm and 10 mm were obtained by the same method as in Example 1. The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 3.

Example 9
The same method as in Example 1 except that 2.5 g of the compound (α1-1) and 2.5 g of dimethyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of 5 g of the compound (α1-1). To obtain polysiloxane xerogel having a thickness of 1 mm and 10 mm. The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 3.

(Comparative Example 1)
Polysiloxane xerogels having a thickness of 1 mm and 10 mm were obtained in the same manner as in Example 1 except that 5 g of methyltrimethoxysilane was used instead of 5 g of compound (α1-1). The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 4.

(Comparative Example 2)
1 g of tetramethoxysilane, 4 g of ethanol, 4 g of water, 0.5 g of urea, and 0.5 g of cetyltrimethylammonium chloride were mixed at room temperature and stirred for 60 minutes to obtain a mixture. A methanol gel was obtained in the same manner as in Example 1 except that this mixture was used. The methanol gel was supercritically dried by the same method as in Example 2 to obtain polysiloxane xerogels having a thickness of 1 mm and 10 mm. The same measurement as in Example 1 was performed on the obtained polysiloxane xerogel. The results are shown in Table 4.

Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2016-228140) filed on November 24, 2016, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

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.

DESCRIPTION OF SYMBOLS 1 Laminated glass 10 1st glass plate 12 2nd glass plate 14 Transparent heat insulation layer 16 1st transparent contact bonding layer 18 2nd transparent contact bonding layer

Claims

It has at least one 6-membered ring selected from the group consisting of a ring structure represented by the following formula (a), a ring structure represented by the following formula (b), and a ring structure represented by the following formula (c). A polysiloxane gel comprising a three-dimensional network structure having a six-membered ring-containing skeleton and a polysiloxane skeleton.

However, * in the formulas (a) to (c) is a bond.
The 6-membered ring-containing skeleton further has a linking group interposed between the 6-membered ring and the polysiloxane skeleton;
The polysiloxane gel according to claim 1, wherein the linking group has at least one group selected from the group consisting of an alkylene group, an oxyalkylene group, a polyether chain, and an arylene group.
The polysiloxane gel according to claim 1, wherein the six-membered ring-containing skeleton has a plurality of bonds, and at least two of the plurality of bonds are bonded to the polysiloxane skeleton. .
The polysiloxane gel according to any one of claims 1 to 3, which is a wet gel further containing a solvent.
The polysiloxane gel according to any one of claims 1 to 3, which is a xerogel.
The polysiloxane gel according to any one of claims 1 to 5, wherein a bending fracture stress is 0.3 MPa or more.
The polysiloxane gel according to any one of claims 1 to 6, wherein a 1 mm-thickness converted value of light transmittance at a wavelength of 500 nm is 50% or more.
It has at least one 6-membered ring selected from the group consisting of a ring structure represented by the following formula (a), a ring structure represented by the following formula (b), and a ring structure represented by the following formula (c). A method for producing a polysiloxane gel containing a three-dimensional network structure having a six-membered ring-containing skeleton and a polysiloxane skeleton,
It has at least one 6-membered ring selected from the group consisting of a ring structure represented by the following formula (a), a ring structure represented by the following formula (b), and a ring structure represented by the following formula (c). A method for producing a polysiloxane gel, wherein a wet gel is obtained by gelling a mixture containing a 6-membered ring-containing silane compound having a 6-membered ring-containing skeleton and a hydrolyzable silyl group, and a solvent.

However, * in the formulas (a) to (c) is a bond.
The 6-membered ring-containing skeleton of the 6-membered ring-containing silane compound further has a linking group interposed between the 6-membered ring and the hydrolyzable silyl group;
The method for producing a polysiloxane gel according to claim 8, wherein the linking group has at least one group selected from the group consisting of an alkylene group, an oxyalkylene group, a polyether chain, and an arylene group.
The method for producing a polysiloxane gel according to claim 8 or 9, wherein the 6-membered ring-containing silane compound has at least two hydrolyzable silyl groups.
The method for producing a polysiloxane gel according to any one of claims 8 to 10, wherein the mixture further contains another silane compound having a hydrolyzable silyl group.
The method for producing a polysiloxane gel according to any one of claims 8 to 11, wherein a xerogel is obtained by removing a solvent from the wet gel.
A heat insulating material comprising the polysiloxane gel according to any one of claims 1 to 7.
Comprising a first glass plate, a second glass plate, and a transparent heat insulation layer present between the first glass plate and the second glass plate,
A laminated glass in which the transparent heat insulating layer is the polysiloxane gel according to any one of claims 1 to 7.