WO2023153252A1 - Coating liquid, method for producing coating liquid, and coating film - Google Patents
Coating liquid, method for producing coating liquid, and coating film Download PDFInfo
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- WO2023153252A1 WO2023153252A1 PCT/JP2023/002782 JP2023002782W WO2023153252A1 WO 2023153252 A1 WO2023153252 A1 WO 2023153252A1 JP 2023002782 W JP2023002782 W JP 2023002782W WO 2023153252 A1 WO2023153252 A1 WO 2023153252A1
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- coating liquid
- water
- soluble polymer
- airgel
- siloxane bond
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Definitions
- the present invention relates to a coating liquid, a method for producing the coating liquid, and a coating film.
- Airgel is known as a material with excellent heat insulation.
- a hydrophobic airgel in a solution of a water-soluble polymer such as polyvinyl alcohol, the compatibility is poor and dispersion becomes difficult. If the airgel is insufficiently dispersed, the physical properties of the coating film after application are significantly affected, and the uneven distribution of the airgel causes a problem that the film strength is lowered and the heat insulation performance is uneven.
- hydrophobic silica airgel particles were dispersed in a water-soluble polymer made hydrophobic by introducing an alkyl group into the hydroxyl group of cellulose.
- a coating liquid has been proposed (see Patent Document 1, for example).
- the object of the present invention is to solve the above-mentioned problems in the past and to achieve the following objects. That is, the present invention is to improve the dispersibility of airgel, prevent the occurrence of powder falling, and provide a coating liquid that can form a coating film having excellent heat insulating performance, a method for producing the coating liquid, and a coating film. and
- the coating liquid according to ⁇ 1> above, wherein the hydrophobic group containing a siloxane bond is represented by either the following general formula (1) or general formula (2).
- R 1 to R 7 represent an alkyl group, a halogenated alkyl group, an aromatic hydrocarbon group, or a trialkylsiloxy group, n is 0 to 10, and m is 0 to 10, l is an integer of 10 or more.
- ⁇ 3> The coating liquid according to any one of ⁇ 1> to ⁇ 2>, wherein the water-soluble polymer contains at least one selected from polyvinyl alcohol, polyacrylic acid, cellulose, chitosan, and alginic acid. . ⁇ 4>
- ⁇ 5> The coating liquid according to any one of ⁇ 1> to ⁇ 4>, wherein the airgel is silica airgel.
- ⁇ 6> The coating liquid according to any one of ⁇ 1> to ⁇ 5>, wherein the content of the airgel is 50% by mass or more based on the total mass of solids in the coating liquid.
- ⁇ 7> Any one of ⁇ 1> to ⁇ 6>, wherein the degree of hydrophobicity of the water-soluble polymer having a hydrophobic group containing a siloxane bond is 5% by mass or less relative to the amount of hydroxyl groups in the water-soluble polymer. It is the described coating liquid.
- ⁇ 8> The coating liquid according to any one of ⁇ 1> to ⁇ 7>, which is for heat insulating materials.
- a method for producing a coating liquid comprising a step of reacting a water-soluble polymer with a compound represented by the following general formula (3) to synthesize a water-soluble polymer having a hydrophobic group containing a siloxane bond.
- R 1 to R 7 represent an alkyl group, a halogenated alkyl group, an aromatic hydrocarbon group, or a trialkylsiloxy group, n is 0 to 10, m is 0 to 10, l is an integer of 10 or more.
- ⁇ 10> a water-soluble polymer having a hydrophobic group containing a siloxane bond; Airgel and a coating film characterized by containing.
- the above-mentioned problems in the conventional art can be solved, the above-mentioned objects can be achieved, the dispersibility of airgel is improved, the occurrence of powder falling can be prevented, and a coating that can form a coating film with excellent heat insulation performance.
- Liquids, methods of making coating liquids, and coatings can be provided.
- the coating liquid of the present invention contains a water-soluble polymer having a hydrophobic group containing a siloxane bond, an aerogel, a liquid medium, and, if necessary, other components.
- the dispersibility of the airgel is greatly improved by containing a water-soluble polymer having a hydrophobic group containing a siloxane bond, the uneven distribution of the airgel is reduced, and there is no powder fallout. Excellent heat insulation.
- a coating film having performance can be formed.
- Water-soluble polymer having a hydrophobic group containing a siloxane bond is not particularly limited as long as it has a hydroxyl group, and can be appropriately selected according to the purpose.
- Water-soluble polymers obtained from algae, algae, tree sap, microbial products, and the like can be used. Among these, polyvinyl alcohol, polyacrylic acid, cellulose, chitosan and alginic acid are preferred, and polyvinyl alcohol and cellulose are particularly preferred.
- the polyvinyl alcohol is a resin containing alcoholic hydroxy groups in the structure of the polymer.
- Polyvinyl alcohol is usually obtained by saponifying a vinyl ester polymer. A portion of the vinyl alcohol units of the polyvinyl alcohol may be modified by reactions such as acetalization, etherification, acetoacetylation, or cationization.
- As said polyvinyl alcohol what was synthesize
- Examples of the cellulose include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, and modified cellulose obtained by further modifying these.
- cellulose what was synthesize
- Examples of the commercially available products include trade name: METOLOSE 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.).
- the hydrophobic group containing a siloxane bond is preferably represented by either the following general formula (1) or general formula (2).
- R 1 to R 7 represent an alkyl group, a halogenated alkyl group, an aromatic hydrocarbon group, or a trialkylsiloxy group
- n is 0 to 10
- m is 0 to 10
- l is an integer of 10 or more.
- the alkyl groups and halogenated alkyl groups of R 1 to R 7 are preferably linear, branched or cyclic and have 1 to 18 carbon atoms.
- aromatic hydrocarbon groups include phenyl groups.
- a phenyl group may have a substituent such as an alkyl group or a hydroxyl group.
- the alkyl group in the trialkylsiloxy group preferably has 1 to 10 carbon atoms.
- a trialkylsiloxy group includes a trimethylsiloxy group.
- l is preferably an integer of 10 or more, more preferably an integer of 10 to 70, from the viewpoint of improving the compatibility of the airgel.
- a water-soluble polymer having a hydrophobic group represented by either the above general formula (1) or general formula (2) can be obtained, for example, by reacting a water-soluble polymer with a compound represented by the following general formula (3).
- R 1 to R 7 represent an alkyl group, a halogenated alkyl group, an aromatic hydrocarbon group, or a trialkylsiloxy group, n is 0 to 10, m is 0 to 10, l is an integer of 10 or more.
- an appropriately synthesized compound may be used, or a commercially available product may be used.
- the commercially available products include epoxy silicone (trade name X-22-173BX, trade name X-22-173DX, manufactured by Shin-Etsu Chemical Co., Ltd.).
- the number average molecular weight (Mn) of the water-soluble polymer having a hydrophobic group containing a siloxane bond is preferably 5,000 or more, more preferably 5,000 or more and 5,000,000 or less, and 10,000 or more and 100,000 or less. More preferred.
- the number average molecular weight (Mn) of the water-soluble polymer can be measured in terms of polystyrene using gel permeation chromatography (GPC).
- Hydrophobicity of the water-soluble polymer having a hydrophobic group containing a siloxane bond is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less relative to the amount of hydroxyl groups.
- the degree of hydrophobicity can be measured by, for example, using 1 H NMR and comparing the integral ratio with silicon-bonded methyl groups derived from hydrophobic groups.
- the content of the water-soluble polymer having a hydrophobic group containing a siloxane bond is, for example, preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass or more, based on the total mass of solids in the coating liquid. is more preferred.
- a dry gel obtained by supercritical drying of a wet gel is called aerogel
- a dry gel obtained by drying under atmospheric pressure is called xerogel
- a dry gel obtained by freeze-drying is called cryogel.
- the resulting low-density dried gel is referred to as an "aerogel” regardless of these drying techniques for wet gels. That is, in the present invention, “aerogel” is aerogel in a broad sense, "Gel comprised of a microporous solid in which the dispersed phase is a gas (a gel composed of a microporous solid in which the dispersed phase is a gas)".
- an airgel has a network-like fine structure, and has a cluster structure in which particulate airgel components of about 2 nm to 20 nm are bonded. There are pores less than 100 nm between the skeletons formed by this cluster structure. As a result, the airgel has a three-dimensional fine porous structure.
- silica airgel which has silica as a main component, for example.
- Hydrophobic silica airgel having a hydrophobic group on the surface is more preferable in order to suppress deterioration in performance of the airgel due to moisture absorption.
- silica airgel is made hydrophobic by bonding a 3-substituted silyl group represented by the following formula to the surface.
- R 1 , R 2 and R 3 may be the same or different and are selected from an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, preferably methyl group, They are an ethyl group, a cyclohexyl group, and a phenyl group.
- the thermal conductivity decreases. Since the airgel surface has a hydrophobic group, even if it is dispersed in an aqueous medium, water is prevented from permeating or penetrating into the pores. This means that the high porosity inherent in the airgel can be maintained even in the state of the coating liquid, and further in the state of the coating film after coating, and thus the excellent heat insulating performance can be exhibited.
- the silica airgel is particulate and preferably has an average particle diameter of 1 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 25 ⁇ m, even more preferably 1 ⁇ m to 10 ⁇ m. If the average particle size is too small, the overall ratio of inter-particle spaces increases, and the ratio of nano-sized pores of silica airgel for heat insulation and sound absorption is low, which is not preferable. On the other hand, if the average particle size is too large, the size of the inter-particle gaps becomes large, and air convection occurs between the large gaps, which is not preferable because there is a possibility that the heat-insulating and sound-absorbing effects are reduced.
- the silica airgel may be appropriately synthesized or may be commercially available. Examples of such commercially available products include trade name MT-1100 (manufactured by Cabot Corporation).
- the airgel content is preferably 70% by mass or more based on the total mass of solids in the coating liquid.
- the content of the airgel is 70% by mass or more, excellent heat insulating performance can be exhibited.
- an aqueous solvent containing water is preferable.
- water pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, distilled water, or ultrapure water can be used.
- the aqueous solvent may contain an organic solvent in addition to water.
- the organic solvent may be any solvent as long as it is compatible with water. Examples include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, and propylene glycol; diethyl ether, tetrahydrofuran, 1,4-dioxane, and the like.
- the content of the liquid medium is not particularly limited, and can be appropriately changed according to the desired viscosity of the coating liquid.
- Other components include, for example, surfactants, thickeners, pigments, leveling agents and the like.
- the method for producing the coating liquid of the present invention includes a step of synthesizing a water-soluble polymer having a hydrophobic group containing a siloxane bond, preferably includes a mixing step, and further includes other steps as necessary.
- a water-soluble polymer having a hydrophobic group containing a siloxane bond can be synthesized by the synthesis method described above.
- the mixing step the water-soluble polymer having hydrophobic groups containing siloxane bonds, the airgel, and optionally other components are mixed in a liquid medium.
- the mixing method is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include shaking, magnetic stirrer stirring, mechanical stirring, vibration stirring, and ultrasonic stirring.
- the coating film of the present invention contains a water-soluble polymer having a hydrophobic group containing a siloxane bond, an airgel, and, if necessary, other components.
- the coating film may be obtained by removing the liquid medium from the coating liquid of the present invention described above. That is, each component in the coating film can be exemplified by the same components as those in the coating liquid described above, and the content of each component in the coating film is the same as the solid content of each component in the coating liquid described above. you can
- the method of applying the coating liquid to the object is not particularly limited and can be appropriately selected according to the purpose. Examples include dip coating, spray coating, spin coating, and roll coating.
- the object to which the coating liquid is applied is not particularly limited.
- the material forming the object may be, for example, metal, ceramic, glass, resin, or a composite material thereof.
- the form of the object can be appropriately selected depending on the purpose of use, material, etc. Examples thereof include block, sheet, powder, and fibrous forms.
- the average thickness of the coating film is not particularly limited, and can be appropriately selected according to the purpose.
- the coating film of the present invention can prevent the occurrence of powder falling off and has excellent heat insulating properties derived from aerogel. It can be widely applied to the construction field, automobile field, home appliance field, semiconductor field, use as a heat insulating material in industrial equipment, etc. In addition to being used as a heat insulating material, the coating film can also be used as a water repellent material, a sound absorbing material, a vibration damping material, a catalyst supporting material, and the like.
- (Synthesis example 1) ⁇ Synthesis of polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond>
- a 10% polyvinyl alcohol aqueous solution (polyvinyl alcohol 1) (trade name: Kuraray Poval 5-88, manufactured by Kuraray Co., Ltd., number average molecular weight : about 2,4000), 0.1 g of caustic soda (sodium hydroxide, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) is added, and 2 g of epoxy silicone (trade name: X-22-173BX, manufactured by Shin-Etsu Chemical Co., Ltd.) is added. The mixture was stirred at 70° C. for 5 hours.
- Synthesis example 2 ⁇ Synthesis of Cellulose 2 Having Hydrophobic Groups Containing Siloxane Bonds>
- the 10% polyvinyl alcohol aqueous solution (trade name: Kuraray Poval 5-88, manufactured by Kuraray Co., Ltd.) was replaced with cellulose 1 (trade name: Metrose 60SH-10000, manufactured by Shin-Etsu Chemical Co., Ltd.)
- cellulose 1 (trade name: Metrose 60SH-10000, manufactured by Shin-Etsu Chemical Co., Ltd.)
- Cellulose 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 2 was obtained in the same manner as in Synthesis Example 1. According to NMR analysis, the hydrophobicity of cellulose 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 2 was 0.2% by mass.
- Example 1 1 g of polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 1 is dissolved in 24 g of distilled water, 5 g of silica airgel (trade name: MT-1100, manufactured by Cabot Corporation) is added, and Awatori Mixer AR is added. -100 (manufactured by Thinky Co., Ltd.) and stirred at 2,000 rpm for 10 minutes to obtain a coating liquid of Example 1.
- silica airgel trade name: MT-1100, manufactured by Cabot Corporation
- Example 2 In Example 1, the procedure was the same as in Example 1 except that the polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was replaced with the cellulose 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 2. Thus, a coating liquid of Example 2 was obtained.
- Example 3 A coating liquid of Example 3 was obtained in the same manner as in Example 1, except that 26 g of distilled water and 3 g of silica airgel (trade name: MT-1100, manufactured by Cabot Corporation) were used.
- Example 4 A coating liquid of Example 4 was obtained in the same manner as in Example 1, except that 28 g of distilled water and 1 g of silica airgel (trade name: MT-1100, manufactured by Cabot Corporation) were used.
- Comparative example 1 Polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was added to a 10% polyvinyl alcohol aqueous solution (polyvinyl alcohol 1) (trade name: Kuraray Poval 5-88, manufactured by Kuraray Co., Ltd., number average A coating liquid of Comparative Example 1 was obtained in the same manner as in Example 1, except that the molecular weight was changed to about 2,4000).
- Comparative example 2 In Example 1, the cellulose 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 2 was replaced with cellulose 1 (trade name: Metolose 60SH-10000, manufactured by Shin-Etsu Chemical Co., Ltd.). Similarly, a coating liquid of Comparative Example 2 was obtained.
- Comparative Example 3 A coating liquid of Comparative Example 3 was prepared in the same manner as in Example 1 except that polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was not added and 25 g of distilled water was used. Obtained.
- Example 4 In Example 1, in the same manner as in Example 1, except that the polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was replaced with the cellulose 3 having an alkyl group (stearyl group) in Synthesis Example 3. , to obtain a coating liquid of Comparative Example 4.
- the cellulose 3 having an alkyl group (stearyl group) in Synthesis Example 3 is a reproduction of Sangelose 90L (manufactured by Daido Kasei Co., Ltd.) used in Example 1 of JP-A-2020-172580. . Introduction of alkyl group (stearyl group) of Sangelose 90L from the product catalog of Daido Kasei Co., Ltd. (http://www.daido-chem.co.jp/topics/view/2, retrieved on February 9, 2022) The ratio (hydrophobicity) is 0.3% by mass to 0.6% by mass.
- a coating film having a size of 200 mm ⁇ 200 mm ⁇ 0.3 mm was prepared using each of the obtained coating liquids, and two plates (heating plate and A cooling plate) was sandwiched between the coating film and the thermal conductivity during heating with a hot plate was measured.
- the coating film of the present invention can prevent the occurrence of powder falling off and has excellent heat insulation derived from aerogel. It can be widely applied to the automotive field, the home appliance field, the semiconductor field, and the use as a heat insulating material in industrial equipment.
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Abstract
Provided is a coating liquid containing: a water-soluble polymer having a hydrophobic group including a siloxane bond; an aerogel; and a liquid medium.
Description
本発明は、塗液、塗液の製造方法、及び塗膜に関する。
The present invention relates to a coating liquid, a method for producing the coating liquid, and a coating film.
断熱性に優れる材料としてエアロゲルが知られている。しかし、ポリビニルアルコール等の水溶性ポリマー溶液に疎水性のエアロゲルを分散させようとしても、相溶性が悪く分散困難な状態になってしまう。エアロゲルの分散が不十分であると塗布後の塗膜の物性に大きく影響を及ぼし、エアロゲルの偏在によって膜強度の低下及び断熱性能のムラが発生してしまうという問題がある。
Airgel is known as a material with excellent heat insulation. However, even if an attempt is made to disperse a hydrophobic airgel in a solution of a water-soluble polymer such as polyvinyl alcohol, the compatibility is poor and dispersion becomes difficult. If the airgel is insufficiently dispersed, the physical properties of the coating film after application are significantly affected, and the uneven distribution of the airgel causes a problem that the film strength is lowered and the heat insulation performance is uneven.
そこで、疎水性のエアロゲルの分散性を改善し、塗膜強度を向上させるため、例えば、セルロースの水酸基にアルキル基を導入して疎水化させた水溶性ポリマーに疎水性シリカエアロゲル粒子を分散させた塗液が提案されている（例えば、特許文献１参照）。
Therefore, in order to improve the dispersibility of the hydrophobic airgel and improve the coating strength, for example, hydrophobic silica airgel particles were dispersed in a water-soluble polymer made hydrophobic by introducing an alkyl group into the hydroxyl group of cellulose. A coating liquid has been proposed (see Patent Document 1, for example).
しかしながら、上記先行技術のようにアルキル基を導入して疎水化した水溶性ポリマーでは、疎水性シリカエアロゲル粒子の分散が十分ではなく、断熱性能のムラが生じたり、塗液を用いて作製した塗膜に触れると粉落ちが発生してしまうという問題がある。
However, in the water-soluble polymer hydrophobized by introducing an alkyl group as in the above prior art, the dispersion of the hydrophobic silica airgel particles is not sufficient, causing uneven heat insulation performance, and the coating prepared using the coating liquid. There is a problem that powder falls off when the film is touched.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、エアロゲルの分散性が向上し、粉落ちの発生を防止でき、断熱性能に優れた塗膜を形成できる塗液、塗液の製造方法、及び塗膜を提供することを目的とする。
The object of the present invention is to solve the above-mentioned problems in the past and to achieve the following objects. That is, the present invention is to improve the dispersibility of airgel, prevent the occurrence of powder falling, and provide a coating liquid that can form a coating film having excellent heat insulating performance, a method for producing the coating liquid, and a coating film. and
前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ シロキサン結合を含む疎水性基を有する水溶性ポリマー、エアロゲル、及び液状媒体を含有することを特徴とする塗液である。
＜２＞ 前記シロキサン結合を含む疎水性基が下記一般式（１）及び一般式（２）のいずれかで表される、前記＜１＞に記載の塗液である。
ただし、前記一般式（１）及び（２）中、Ｒ１～Ｒ７はアルキル基、ハロゲン化アルキル基、芳香族炭化水素基、又はトリアルキルシロキシ基を表し、ｎは０～１０、ｍは０～１０、ｌは１０以上の整数である。
＜３＞ 前記水溶性ポリマーが、ポリビニルアルコール、ポリアクリル酸、セルロース、キトサン、及びアルギン酸から選択される少なくとも１種を含む、前記＜１＞から＜２＞のいずれかに記載の塗液である。
＜４＞ 前記シロキサン結合を含む疎水性基を有する水溶性ポリマーの数平均分子量が５,０００以上である、前記＜１＞から＜３＞のいずれかに記載の塗液である。
＜５＞ 前記エアロゲルがシリカエアロゲルである、前記＜１＞から＜４＞のいずれかに記載の塗液である。
＜６＞ 前記エアロゲルの含有量が塗液中の固形分の全質量基準で、５０質量％以上である、前記＜１＞から＜５＞のいずれかに記載の塗液である。
＜７＞ 前記シロキサン結合を含む疎水性基を有する水溶性ポリマーの疎水化度が、水溶性ポリマーの水酸基量に対して５質量％以下である、前記＜１＞から＜６＞のいずれかに記載の塗液である。
＜８＞ 断熱材用である、前記＜１＞から＜７＞のいずれかに記載の塗液である。
＜９＞ 前記＜１＞から＜８＞のいずれかに記載の塗液の製造方法であって、
水溶性ポリマーと下記一般式（３）で表される化合物を反応させてシロキサン結合を含む疎水性基を有する水溶性ポリマーを合成する工程を含むことを特徴とする塗液の製造方法である。
ただし、前記一般式（３）中、Ｒ１～Ｒ７はアルキル基、ハロゲン化アルキル基、芳香族炭化水素基、又はトリアルキルシロキシ基を表し、ｎは０～１０、ｍは０～１０、ｌは１０以上の整数である。
＜１０＞ シロキサン結合を含む疎水性基を有する水溶性ポリマーと、
エアロゲルと、を含有することを特徴とする塗膜である。 Means for solving the above problems are as follows. Namely
<1> A coating liquid characterized by containing a water-soluble polymer having a hydrophobic group containing a siloxane bond, an airgel, and a liquid medium.
<2> The coating liquid according to <1> above, wherein the hydrophobic group containing a siloxane bond is represented by either the following general formula (1) or general formula (2).
However, in the general formulas (1) and (2), R 1 to R 7 represent an alkyl group, a halogenated alkyl group, an aromatic hydrocarbon group, or a trialkylsiloxy group, n is 0 to 10, and m is 0 to 10, l is an integer of 10 or more.
<3> The coating liquid according to any one of <1> to <2>, wherein the water-soluble polymer contains at least one selected from polyvinyl alcohol, polyacrylic acid, cellulose, chitosan, and alginic acid. .
<4> The coating liquid according to any one of <1> to <3>, wherein the water-soluble polymer having a hydrophobic group containing a siloxane bond has a number average molecular weight of 5,000 or more.
<5> The coating liquid according to any one of <1> to <4>, wherein the airgel is silica airgel.
<6> The coating liquid according to any one of <1> to <5>, wherein the content of the airgel is 50% by mass or more based on the total mass of solids in the coating liquid.
<7> Any one of <1> to <6>, wherein the degree of hydrophobicity of the water-soluble polymer having a hydrophobic group containing a siloxane bond is 5% by mass or less relative to the amount of hydroxyl groups in the water-soluble polymer. It is the described coating liquid.
<8> The coating liquid according to any one of <1> to <7>, which is for heat insulating materials.
<9> The method for producing a coating liquid according to any one of <1> to <8>,
A method for producing a coating liquid, comprising a step of reacting a water-soluble polymer with a compound represented by the following general formula (3) to synthesize a water-soluble polymer having a hydrophobic group containing a siloxane bond.
However, in the general formula (3), R 1 to R 7 represent an alkyl group, a halogenated alkyl group, an aromatic hydrocarbon group, or a trialkylsiloxy group, n is 0 to 10, m is 0 to 10, l is an integer of 10 or more.
<10> a water-soluble polymer having a hydrophobic group containing a siloxane bond;
Airgel and a coating film characterized by containing.
＜１＞ シロキサン結合を含む疎水性基を有する水溶性ポリマー、エアロゲル、及び液状媒体を含有することを特徴とする塗液である。
＜２＞ 前記シロキサン結合を含む疎水性基が下記一般式（１）及び一般式（２）のいずれかで表される、前記＜１＞に記載の塗液である。
＜３＞ 前記水溶性ポリマーが、ポリビニルアルコール、ポリアクリル酸、セルロース、キトサン、及びアルギン酸から選択される少なくとも１種を含む、前記＜１＞から＜２＞のいずれかに記載の塗液である。
＜４＞ 前記シロキサン結合を含む疎水性基を有する水溶性ポリマーの数平均分子量が５,０００以上である、前記＜１＞から＜３＞のいずれかに記載の塗液である。
＜５＞ 前記エアロゲルがシリカエアロゲルである、前記＜１＞から＜４＞のいずれかに記載の塗液である。
＜６＞ 前記エアロゲルの含有量が塗液中の固形分の全質量基準で、５０質量％以上である、前記＜１＞から＜５＞のいずれかに記載の塗液である。
＜７＞ 前記シロキサン結合を含む疎水性基を有する水溶性ポリマーの疎水化度が、水溶性ポリマーの水酸基量に対して５質量％以下である、前記＜１＞から＜６＞のいずれかに記載の塗液である。
＜８＞ 断熱材用である、前記＜１＞から＜７＞のいずれかに記載の塗液である。
＜９＞ 前記＜１＞から＜８＞のいずれかに記載の塗液の製造方法であって、
水溶性ポリマーと下記一般式（３）で表される化合物を反応させてシロキサン結合を含む疎水性基を有する水溶性ポリマーを合成する工程を含むことを特徴とする塗液の製造方法である。
＜１０＞ シロキサン結合を含む疎水性基を有する水溶性ポリマーと、
エアロゲルと、を含有することを特徴とする塗膜である。 Means for solving the above problems are as follows. Namely
<1> A coating liquid characterized by containing a water-soluble polymer having a hydrophobic group containing a siloxane bond, an airgel, and a liquid medium.
<2> The coating liquid according to <1> above, wherein the hydrophobic group containing a siloxane bond is represented by either the following general formula (1) or general formula (2).
<3> The coating liquid according to any one of <1> to <2>, wherein the water-soluble polymer contains at least one selected from polyvinyl alcohol, polyacrylic acid, cellulose, chitosan, and alginic acid. .
<4> The coating liquid according to any one of <1> to <3>, wherein the water-soluble polymer having a hydrophobic group containing a siloxane bond has a number average molecular weight of 5,000 or more.
<5> The coating liquid according to any one of <1> to <4>, wherein the airgel is silica airgel.
<6> The coating liquid according to any one of <1> to <5>, wherein the content of the airgel is 50% by mass or more based on the total mass of solids in the coating liquid.
<7> Any one of <1> to <6>, wherein the degree of hydrophobicity of the water-soluble polymer having a hydrophobic group containing a siloxane bond is 5% by mass or less relative to the amount of hydroxyl groups in the water-soluble polymer. It is the described coating liquid.
<8> The coating liquid according to any one of <1> to <7>, which is for heat insulating materials.
<9> The method for producing a coating liquid according to any one of <1> to <8>,
A method for producing a coating liquid, comprising a step of reacting a water-soluble polymer with a compound represented by the following general formula (3) to synthesize a water-soluble polymer having a hydrophobic group containing a siloxane bond.
<10> a water-soluble polymer having a hydrophobic group containing a siloxane bond;
Airgel and a coating film characterized by containing.
本発明によると、従来における前記諸問題を解決し、前記目的を達成することができ、エアロゲルの分散性が向上し、粉落ちの発生を防止でき、断熱性能に優れた塗膜を形成できる塗液、塗液の製造方法、及び塗膜を提供することができる。
According to the present invention, the above-mentioned problems in the conventional art can be solved, the above-mentioned objects can be achieved, the dispersibility of airgel is improved, the occurrence of powder falling can be prevented, and a coating that can form a coating film with excellent heat insulation performance. Liquids, methods of making coating liquids, and coatings can be provided.
（塗液）
本発明の塗液は、シロキサン結合を含む疎水性基を有する水溶性ポリマー、エアロゲル、及び液状媒体を含有し、更に必要に応じてその他の成分を含有する。 (Coating liquid)
The coating liquid of the present invention contains a water-soluble polymer having a hydrophobic group containing a siloxane bond, an aerogel, a liquid medium, and, if necessary, other components.
本発明の塗液は、シロキサン結合を含む疎水性基を有する水溶性ポリマー、エアロゲル、及び液状媒体を含有し、更に必要に応じてその他の成分を含有する。 (Coating liquid)
The coating liquid of the present invention contains a water-soluble polymer having a hydrophobic group containing a siloxane bond, an aerogel, a liquid medium, and, if necessary, other components.
本発明においては、シロキサン結合を含む疎水性基を有する水溶性ポリマーを含有することによってエアロゲルの分散性が大幅に向上するため、エアロゲルの偏在が少なくなり、粉落ちの発生がない、優れた断熱性能を有する塗膜を形成できる。
In the present invention, since the dispersibility of the airgel is greatly improved by containing a water-soluble polymer having a hydrophobic group containing a siloxane bond, the uneven distribution of the airgel is reduced, and there is no powder fallout. Excellent heat insulation. A coating film having performance can be formed.
＜シロキサン結合を含む疎水性基を有する水溶性ポリマー＞
シロキサン結合を含む疎水性基を有する水溶性ポリマーにおける水溶性ポリマーとしては、水酸基を有するものであれば特に制限はなく、目的に応じて適宜選択することができ、例えば、合成物、動植物、魚介類、海藻、樹液、微生物産出物などから得られる水溶性ポリマーを用いることができる。これらの中でも、ポリビニルアルコール、ポリアクリル酸、セルロース、キトサン、アルギン酸が好ましく、ポリビニルアルコール、セルロースが特に好ましい。 <Water-soluble polymer having a hydrophobic group containing a siloxane bond>
The water-soluble polymer in the water-soluble polymer having a hydrophobic group containing a siloxane bond is not particularly limited as long as it has a hydroxyl group, and can be appropriately selected according to the purpose. Water-soluble polymers obtained from algae, algae, tree sap, microbial products, and the like can be used. Among these, polyvinyl alcohol, polyacrylic acid, cellulose, chitosan and alginic acid are preferred, and polyvinyl alcohol and cellulose are particularly preferred.
シロキサン結合を含む疎水性基を有する水溶性ポリマーにおける水溶性ポリマーとしては、水酸基を有するものであれば特に制限はなく、目的に応じて適宜選択することができ、例えば、合成物、動植物、魚介類、海藻、樹液、微生物産出物などから得られる水溶性ポリマーを用いることができる。これらの中でも、ポリビニルアルコール、ポリアクリル酸、セルロース、キトサン、アルギン酸が好ましく、ポリビニルアルコール、セルロースが特に好ましい。 <Water-soluble polymer having a hydrophobic group containing a siloxane bond>
The water-soluble polymer in the water-soluble polymer having a hydrophobic group containing a siloxane bond is not particularly limited as long as it has a hydroxyl group, and can be appropriately selected according to the purpose. Water-soluble polymers obtained from algae, algae, tree sap, microbial products, and the like can be used. Among these, polyvinyl alcohol, polyacrylic acid, cellulose, chitosan and alginic acid are preferred, and polyvinyl alcohol and cellulose are particularly preferred.
前記ポリビニルアルコールは、ポリマーの構造中にアルコール性ヒドロキシ基を含有する樹脂である。ポリビニルアルコールは、通常、ビニルエステル系重合体をケン化することにより得られるものである。
前記ポリビニルアルコールは、ビニルアルコール単位の一部が、アセタール化、エーテル化、アセトアセチル化、又はカチオン化等の反応によって、変性されたものであってもよい。
前記ポリビニルアルコールとしては、適宜合成したものを使用してもよいし、市販品を使用してもよい。前記市販品としては、例えば、商品名：クラレポバール ５－８８（株式会社クラレ製）などが挙げられる。 The polyvinyl alcohol is a resin containing alcoholic hydroxy groups in the structure of the polymer. Polyvinyl alcohol is usually obtained by saponifying a vinyl ester polymer.
A portion of the vinyl alcohol units of the polyvinyl alcohol may be modified by reactions such as acetalization, etherification, acetoacetylation, or cationization.
As said polyvinyl alcohol, what was synthesize|combined suitably may be used, and a commercial item may be used. Examples of the commercially available products include trade name: Kuraray Poval 5-88 (manufactured by Kuraray Co., Ltd.).
前記ポリビニルアルコールは、ビニルアルコール単位の一部が、アセタール化、エーテル化、アセトアセチル化、又はカチオン化等の反応によって、変性されたものであってもよい。
前記ポリビニルアルコールとしては、適宜合成したものを使用してもよいし、市販品を使用してもよい。前記市販品としては、例えば、商品名：クラレポバール ５－８８（株式会社クラレ製）などが挙げられる。 The polyvinyl alcohol is a resin containing alcoholic hydroxy groups in the structure of the polymer. Polyvinyl alcohol is usually obtained by saponifying a vinyl ester polymer.
A portion of the vinyl alcohol units of the polyvinyl alcohol may be modified by reactions such as acetalization, etherification, acetoacetylation, or cationization.
As said polyvinyl alcohol, what was synthesize|combined suitably may be used, and a commercial item may be used. Examples of the commercially available products include trade name: Kuraray Poval 5-88 (manufactured by Kuraray Co., Ltd.).
前記セルロースとしては、例えば、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース、又はこれらを更に変性した変性セルロースなどが挙げられる。
前記セルロースとしては、適宜合成したものを使用してもよいし、市販品を使用してもよい。前記市販品としては、例えば、商品名：メトローズ ６０ＳＨ－１００００（信越化学工業株式会社製）などが挙げられる。 Examples of the cellulose include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, and modified cellulose obtained by further modifying these.
As said cellulose, what was synthesize|combined suitably may be used, and a commercial item may be used. Examples of the commercially available products include trade name: METOLOSE 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.).
前記セルロースとしては、適宜合成したものを使用してもよいし、市販品を使用してもよい。前記市販品としては、例えば、商品名：メトローズ ６０ＳＨ－１００００（信越化学工業株式会社製）などが挙げられる。 Examples of the cellulose include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, and modified cellulose obtained by further modifying these.
As said cellulose, what was synthesize|combined suitably may be used, and a commercial item may be used. Examples of the commercially available products include trade name: METOLOSE 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.).
前記シロキサン結合を含む疎水性基としては、下記一般式（１）及び一般式（２）のいずれかで表されるものが好ましい。シロキサン結合を含む疎水性基を水溶性ポリマーの側鎖に導入することで、疎水性シリカエアロゲルとの相溶性を向上させることができる。
The hydrophobic group containing a siloxane bond is preferably represented by either the following general formula (1) or general formula (2). By introducing a hydrophobic group containing a siloxane bond to the side chain of the water-soluble polymer, the compatibility with the hydrophobic silica airgel can be improved.
Ｒ１～Ｒ７のアルキル基及びハロゲン化アルキル基は、直鎖、分岐鎖、又は環状の炭素数１～１８が好ましい。
芳香族炭化水素基としては、例えば、フェニル基などが挙げられる。フェニル基はアルキル基、水酸基等の置換基を有していてもよい。
トリアルキルシロキシ基におけるアルキル基は炭素数１～１０が好ましい。トリアルキルシロキシ基としては、トリメチルシロキシ基などが挙げられる。
ｌはエアロゲルの相溶性を向上させる点から、１０以上の整数が好ましく、１０～７０の整数がより好ましい。
The alkyl groups and halogenated alkyl groups of R 1 to R 7 are preferably linear, branched or cyclic and have 1 to 18 carbon atoms.
Examples of aromatic hydrocarbon groups include phenyl groups. A phenyl group may have a substituent such as an alkyl group or a hydroxyl group.
The alkyl group in the trialkylsiloxy group preferably has 1 to 10 carbon atoms. A trialkylsiloxy group includes a trimethylsiloxy group.
l is preferably an integer of 10 or more, more preferably an integer of 10 to 70, from the viewpoint of improving the compatibility of the airgel.
上記一般式（１）及び一般式（２）のいずれかで表される疎水性基を有する水溶性ポリマーは、例えば、水溶性ポリマーと下記一般式（３）で表される化合物を反応させることにより合成することができる。水溶性ポリマーの水酸基と一般式（３）で表される化合物のエポキシ基とを反応させることにより、水溶性ポリマーの側鎖に上記一般式（１）又は（２）で表されるシロキサン結合を含む疎水性基が導入される。
A water-soluble polymer having a hydrophobic group represented by either the above general formula (1) or general formula (2) can be obtained, for example, by reacting a water-soluble polymer with a compound represented by the following general formula (3). can be synthesized by By reacting the hydroxyl group of the water-soluble polymer with the epoxy group of the compound represented by the general formula (3), the siloxane bond represented by the above general formula (1) or (2) is formed in the side chain of the water-soluble polymer. Hydrophobic groups containing are introduced.
前記一般式（３）で表される化合物としては、適宜合成したものを使用してもよいし、市販品を使用してもよい。前記市販品としては、例えば、エポキシシリコーン（商品名Ｘ－２２－１７３ＢＸ、商品名Ｘ－２２－１７３ＤＸ、信越化学工業株式会社製）などが挙げられる。
なお、本発明者は、商品名「Ｘ－２２－１７３ＢＸ」（信越化学工業株式会社製）をＮＭＲ、ＩＲで分析して、上記一般式（３）において、Ｒ１～Ｒ３がメチル基、Ｒ４がブチル基、Ｒ５～Ｒ７がメチル基、ｎ＝１、ｍ＝３、ｌ＝３２であることを確認している。
また、商品名「Ｘ－２２－１７３ＤＸ」（信越化学工業株式会社製）をＮＭＲ、ＩＲで分析して、上記一般式（３）において、Ｒ１～Ｒ３がメチル基、Ｒ４がブチル基、Ｒ５～Ｒ７がメチル基、ｎ＝１、ｍ＝３、ｌ＝６３であることを確認している。 As the compound represented by the general formula (3), an appropriately synthesized compound may be used, or a commercially available product may be used. Examples of the commercially available products include epoxy silicone (trade name X-22-173BX, trade name X-22-173DX, manufactured by Shin-Etsu Chemical Co., Ltd.).
The present inventor analyzed the product name "X-22-173BX" (manufactured by Shin-Etsu Chemical Co., Ltd.) by NMR and IR, and found that in the above general formula (3), R 1 to R 3 are methyl groups, It has been confirmed that R 4 is a butyl group, R 5 to R 7 are methyl groups, n=1, m=3, and l=32.
Further, the product name "X-22-173DX " (manufactured by Shin-Etsu Chemical Co., Ltd.) was analyzed by NMR and IR. , R 5 to R 7 are methyl groups, n=1, m=3, l=63.
なお、本発明者は、商品名「Ｘ－２２－１７３ＢＸ」（信越化学工業株式会社製）をＮＭＲ、ＩＲで分析して、上記一般式（３）において、Ｒ１～Ｒ３がメチル基、Ｒ４がブチル基、Ｒ５～Ｒ７がメチル基、ｎ＝１、ｍ＝３、ｌ＝３２であることを確認している。
また、商品名「Ｘ－２２－１７３ＤＸ」（信越化学工業株式会社製）をＮＭＲ、ＩＲで分析して、上記一般式（３）において、Ｒ１～Ｒ３がメチル基、Ｒ４がブチル基、Ｒ５～Ｒ７がメチル基、ｎ＝１、ｍ＝３、ｌ＝６３であることを確認している。 As the compound represented by the general formula (3), an appropriately synthesized compound may be used, or a commercially available product may be used. Examples of the commercially available products include epoxy silicone (trade name X-22-173BX, trade name X-22-173DX, manufactured by Shin-Etsu Chemical Co., Ltd.).
The present inventor analyzed the product name "X-22-173BX" (manufactured by Shin-Etsu Chemical Co., Ltd.) by NMR and IR, and found that in the above general formula (3), R 1 to R 3 are methyl groups, It has been confirmed that R 4 is a butyl group, R 5 to R 7 are methyl groups, n=1, m=3, and l=32.
Further, the product name "X-22-173DX " (manufactured by Shin-Etsu Chemical Co., Ltd.) was analyzed by NMR and IR. , R 5 to R 7 are methyl groups, n=1, m=3, l=63.
シロキサン結合を含む疎水性基を有する水溶性ポリマーの数平均分子量（Ｍｎ）は５,０００以上が好ましく、５，０００以上５，０００，０００以下がより好ましく、１０,０００以上１００，０００以下が更に好ましい。
前記水溶性ポリマーの数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用い、ポリスチレン換算で測定することができる。 The number average molecular weight (Mn) of the water-soluble polymer having a hydrophobic group containing a siloxane bond is preferably 5,000 or more, more preferably 5,000 or more and 5,000,000 or less, and 10,000 or more and 100,000 or less. More preferred.
The number average molecular weight (Mn) of the water-soluble polymer can be measured in terms of polystyrene using gel permeation chromatography (GPC).
前記水溶性ポリマーの数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用い、ポリスチレン換算で測定することができる。 The number average molecular weight (Mn) of the water-soluble polymer having a hydrophobic group containing a siloxane bond is preferably 5,000 or more, more preferably 5,000 or more and 5,000,000 or less, and 10,000 or more and 100,000 or less. More preferred.
The number average molecular weight (Mn) of the water-soluble polymer can be measured in terms of polystyrene using gel permeation chromatography (GPC).
シロキサン結合を含む疎水性基を有する水溶性ポリマーの疎水化度は水酸基量に対して５質量％以下が好ましく、１質量％以下がより好ましく、０．５質量％以下が更に好ましい。
前記疎水化度は、例えば、１Ｈ ＮＭＲを用いて、疎水性基由来であるケイ素に結合したメチル基との積分比を比較することにより測定することができる。 Hydrophobicity of the water-soluble polymer having a hydrophobic group containing a siloxane bond is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less relative to the amount of hydroxyl groups.
The degree of hydrophobicity can be measured by, for example, using 1 H NMR and comparing the integral ratio with silicon-bonded methyl groups derived from hydrophobic groups.
前記疎水化度は、例えば、１Ｈ ＮＭＲを用いて、疎水性基由来であるケイ素に結合したメチル基との積分比を比較することにより測定することができる。 Hydrophobicity of the water-soluble polymer having a hydrophobic group containing a siloxane bond is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less relative to the amount of hydroxyl groups.
The degree of hydrophobicity can be measured by, for example, using 1 H NMR and comparing the integral ratio with silicon-bonded methyl groups derived from hydrophobic groups.
シロキサン結合を含む疎水性基を有する水溶性ポリマーの含有量は、塗液中の固形分の全質量基準で、例えば、１質量％以上が好ましく、５質量％以上がより好ましく、１０質量％以上が更に好ましい。
The content of the water-soluble polymer having a hydrophobic group containing a siloxane bond is, for example, preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass or more, based on the total mass of solids in the coating liquid. is more preferred.
＜エアロゲル＞
狭義には、湿潤ゲルに対して超臨界乾燥法を用いて得られた乾燥ゲルをエアロゲル、大気圧下での乾燥により得られた乾燥ゲルをキセロゲル、凍結乾燥により得られた乾燥ゲルをクライオゲルと称するが、本実施形態においては、湿潤ゲルのこれらの乾燥手法によらず、得られた低密度の乾燥ゲルを「エアロゲル」と称する。即ち、本発明において、「エアロゲル」とは、広義のエアロゲルである「Ｇｅｌ ｃｏｍｐｒｉｓｅｄ ｏｆ ａ ｍｉｃｒｏｐｏｒｏｕｓ ｓｏｌｉｄ ｉｎ ｗｈｉｃｈ ｔｈｅ ｄｉｓｐｅｒｓｅｄ ｐｈａｓｅ ｉｓ ａ ｇａｓ（分散相が気体である微多孔性固体から構成されるゲル）」を意味する。一般的に、エアロゲルの内部は、網目状の微細構造を有しており、２ｎｍ～２０ｎｍ程度の粒子状のエアロゲル成分が結合したクラスター構造を有している。このクラスター構造により形成される骨格間には、１００ｎｍに満たない細孔がある。これにより、エアロゲルは、三次元的に微細な多孔性の構造が形成されている。 <Aerogel>
In a narrow sense, a dry gel obtained by supercritical drying of a wet gel is called aerogel, a dry gel obtained by drying under atmospheric pressure is called xerogel, and a dry gel obtained by freeze-drying is called cryogel. However, in the present embodiment, the resulting low-density dried gel is referred to as an "aerogel" regardless of these drying techniques for wet gels. That is, in the present invention, "aerogel" is aerogel in a broad sense, "Gel comprised of a microporous solid in which the dispersed phase is a gas (a gel composed of a microporous solid in which the dispersed phase is a gas)". means In general, the inside of an airgel has a network-like fine structure, and has a cluster structure in which particulate airgel components of about 2 nm to 20 nm are bonded. There are pores less than 100 nm between the skeletons formed by this cluster structure. As a result, the airgel has a three-dimensional fine porous structure.
狭義には、湿潤ゲルに対して超臨界乾燥法を用いて得られた乾燥ゲルをエアロゲル、大気圧下での乾燥により得られた乾燥ゲルをキセロゲル、凍結乾燥により得られた乾燥ゲルをクライオゲルと称するが、本実施形態においては、湿潤ゲルのこれらの乾燥手法によらず、得られた低密度の乾燥ゲルを「エアロゲル」と称する。即ち、本発明において、「エアロゲル」とは、広義のエアロゲルである「Ｇｅｌ ｃｏｍｐｒｉｓｅｄ ｏｆ ａ ｍｉｃｒｏｐｏｒｏｕｓ ｓｏｌｉｄ ｉｎ ｗｈｉｃｈ ｔｈｅ ｄｉｓｐｅｒｓｅｄ ｐｈａｓｅ ｉｓ ａ ｇａｓ（分散相が気体である微多孔性固体から構成されるゲル）」を意味する。一般的に、エアロゲルの内部は、網目状の微細構造を有しており、２ｎｍ～２０ｎｍ程度の粒子状のエアロゲル成分が結合したクラスター構造を有している。このクラスター構造により形成される骨格間には、１００ｎｍに満たない細孔がある。これにより、エアロゲルは、三次元的に微細な多孔性の構造が形成されている。 <Aerogel>
In a narrow sense, a dry gel obtained by supercritical drying of a wet gel is called aerogel, a dry gel obtained by drying under atmospheric pressure is called xerogel, and a dry gel obtained by freeze-drying is called cryogel. However, in the present embodiment, the resulting low-density dried gel is referred to as an "aerogel" regardless of these drying techniques for wet gels. That is, in the present invention, "aerogel" is aerogel in a broad sense, "Gel comprised of a microporous solid in which the dispersed phase is a gas (a gel composed of a microporous solid in which the dispersed phase is a gas)". means In general, the inside of an airgel has a network-like fine structure, and has a cluster structure in which particulate airgel components of about 2 nm to 20 nm are bonded. There are pores less than 100 nm between the skeletons formed by this cluster structure. As a result, the airgel has a three-dimensional fine porous structure.
前記エアロゲルとしては、例えば、シリカを主成分とするシリカエアロゲルであることが好ましい。吸湿によるエアロゲルの性能低下を抑制するため、表面に疎水性基を有する疎水性シリカエアロゲルがより好ましい。具体的には、シリカエアロゲルは表面に、下記式で表わされる３置換シリル基が結合することにより疎水性となっている。式中、Ｒ１、Ｒ２、Ｒ３は同一であっても異なっていてもよく、炭素数１～１８のアルキル基、又は炭素数６～１８のアリール基から選ばれ、好ましくはメチル基、エチル基、シクロヘキシル基、フェニル基である。
As said airgel, it is preferable that it is a silica airgel which has silica as a main component, for example. Hydrophobic silica airgel having a hydrophobic group on the surface is more preferable in order to suppress deterioration in performance of the airgel due to moisture absorption. Specifically, silica airgel is made hydrophobic by bonding a 3-substituted silyl group represented by the following formula to the surface. In the formula, R 1 , R 2 and R 3 may be the same or different and are selected from an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, preferably methyl group, They are an ethyl group, a cyclohexyl group, and a phenyl group.
前記エアロゲルは、気孔率の増加に伴って、平均自由行程を阻害する数１０ｎｍの空気孔が多くなるので、熱伝導率が小さくなる。エアロゲル表面に疎水性基を有することから、水性媒体中に分散しても、細孔内への水の染み込みや侵入が防止される。このことは、塗液の状態、更には塗布後の塗膜の状態においても、エアロゲル本来の高い気孔率を保持できること、ひいては優れた断熱性能を発揮できることを意味する。
As the porosity of the airgel increases, the number of air holes of several tens of nanometers that impede the mean free path increases, so the thermal conductivity decreases. Since the airgel surface has a hydrophobic group, even if it is dispersed in an aqueous medium, water is prevented from permeating or penetrating into the pores. This means that the high porosity inherent in the airgel can be maintained even in the state of the coating liquid, and further in the state of the coating film after coating, and thus the excellent heat insulating performance can be exhibited.
前記シリカエアロゲルは、粒子状であり、平均粒子径は１μｍ以上５０μｍ以下が好ましく、１μｍ以上２５μｍ以下がより好ましく、１μｍ以上１０μｍ以下が更に好ましい。
前記平均粒子径が小さすぎると粒子間隙総合比が増え、断熱や吸音等シリカエアロゲルのナノサイズ細孔の比率が少ないため好ましくない。一方、平均粒子径が大きすぎると、粒子間隙のサイズが大きくなり大きい空隙の間に空気が対流し断熱と吸音効果が減る恐れがあるため好ましくない。 The silica airgel is particulate and preferably has an average particle diameter of 1 μm to 50 μm, more preferably 1 μm to 25 μm, even more preferably 1 μm to 10 μm.
If the average particle size is too small, the overall ratio of inter-particle spaces increases, and the ratio of nano-sized pores of silica airgel for heat insulation and sound absorption is low, which is not preferable. On the other hand, if the average particle size is too large, the size of the inter-particle gaps becomes large, and air convection occurs between the large gaps, which is not preferable because there is a possibility that the heat-insulating and sound-absorbing effects are reduced.
前記平均粒子径が小さすぎると粒子間隙総合比が増え、断熱や吸音等シリカエアロゲルのナノサイズ細孔の比率が少ないため好ましくない。一方、平均粒子径が大きすぎると、粒子間隙のサイズが大きくなり大きい空隙の間に空気が対流し断熱と吸音効果が減る恐れがあるため好ましくない。 The silica airgel is particulate and preferably has an average particle diameter of 1 μm to 50 μm, more preferably 1 μm to 25 μm, even more preferably 1 μm to 10 μm.
If the average particle size is too small, the overall ratio of inter-particle spaces increases, and the ratio of nano-sized pores of silica airgel for heat insulation and sound absorption is low, which is not preferable. On the other hand, if the average particle size is too large, the size of the inter-particle gaps becomes large, and air convection occurs between the large gaps, which is not preferable because there is a possibility that the heat-insulating and sound-absorbing effects are reduced.
前記シリカエアロゲルは、適宜合成したものを使用してもよいし、市販品を使用してもよい。該市販品としては、例えば、商品名ＭＴ－１１００（キャボット社製）などが挙げられる。
The silica airgel may be appropriately synthesized or may be commercially available. Examples of such commercially available products include trade name MT-1100 (manufactured by Cabot Corporation).
エアロゲルの含有量は、塗液中の固形分の全質量基準で、７０質量％以上が好ましい。
前記エアロゲルの含有量が７０質量％以上であると、優れた断熱性能を発揮することができる。 The airgel content is preferably 70% by mass or more based on the total mass of solids in the coating liquid.
When the content of the airgel is 70% by mass or more, excellent heat insulating performance can be exhibited.
前記エアロゲルの含有量が７０質量％以上であると、優れた断熱性能を発揮することができる。 The airgel content is preferably 70% by mass or more based on the total mass of solids in the coating liquid.
When the content of the airgel is 70% by mass or more, excellent heat insulating performance can be exhibited.
＜液状媒体＞
液状媒体としては、水を含む水系溶媒が好ましい。水としては、イオン交換水、限外濾過水、逆浸透水、蒸留水等の純水、又は超純水を用いることができる。
前記水系溶媒には、水以外に有機溶媒が含まれていてもよい。前記有機溶媒としては、水との相溶性を有するものであればよく、例えば、メタノール、エタノール、イソプロパノール、ブタノール、エチレングリコール、プロピレングリコール等のアルコール類；ジエチルエーテル、テトラヒドロフラン、１，４－ジオキサン等のエーテル類；アセトン、メチルエチルケトン等のケトン類；酢酸、プロピオン酸等のカルボン酸；アセトニトリル、ジメチルホルムアミド、トリエチルアミン等の窒素含有化合物などが挙げられる。
本発明の塗液において、液状媒体の含有量は特に限定されず、所望の塗液の粘度等に応じて適宜変更することができる。 <Liquid medium>
As the liquid medium, an aqueous solvent containing water is preferable. As water, pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, distilled water, or ultrapure water can be used.
The aqueous solvent may contain an organic solvent in addition to water. The organic solvent may be any solvent as long as it is compatible with water. Examples include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, and propylene glycol; diethyl ether, tetrahydrofuran, 1,4-dioxane, and the like. ketones such as acetone and methyl ethyl ketone; carboxylic acids such as acetic acid and propionic acid; and nitrogen-containing compounds such as acetonitrile, dimethylformamide and triethylamine.
In the coating liquid of the present invention, the content of the liquid medium is not particularly limited, and can be appropriately changed according to the desired viscosity of the coating liquid.
液状媒体としては、水を含む水系溶媒が好ましい。水としては、イオン交換水、限外濾過水、逆浸透水、蒸留水等の純水、又は超純水を用いることができる。
前記水系溶媒には、水以外に有機溶媒が含まれていてもよい。前記有機溶媒としては、水との相溶性を有するものであればよく、例えば、メタノール、エタノール、イソプロパノール、ブタノール、エチレングリコール、プロピレングリコール等のアルコール類；ジエチルエーテル、テトラヒドロフラン、１，４－ジオキサン等のエーテル類；アセトン、メチルエチルケトン等のケトン類；酢酸、プロピオン酸等のカルボン酸；アセトニトリル、ジメチルホルムアミド、トリエチルアミン等の窒素含有化合物などが挙げられる。
本発明の塗液において、液状媒体の含有量は特に限定されず、所望の塗液の粘度等に応じて適宜変更することができる。 <Liquid medium>
As the liquid medium, an aqueous solvent containing water is preferable. As water, pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, distilled water, or ultrapure water can be used.
The aqueous solvent may contain an organic solvent in addition to water. The organic solvent may be any solvent as long as it is compatible with water. Examples include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, and propylene glycol; diethyl ether, tetrahydrofuran, 1,4-dioxane, and the like. ketones such as acetone and methyl ethyl ketone; carboxylic acids such as acetic acid and propionic acid; and nitrogen-containing compounds such as acetonitrile, dimethylformamide and triethylamine.
In the coating liquid of the present invention, the content of the liquid medium is not particularly limited, and can be appropriately changed according to the desired viscosity of the coating liquid.
＜その他の成分＞
その他の成分としては、例えば、界面活性剤、増粘剤、顔料、レベリング剤などが挙げられる。 <Other ingredients>
Other components include, for example, surfactants, thickeners, pigments, leveling agents and the like.
その他の成分としては、例えば、界面活性剤、増粘剤、顔料、レベリング剤などが挙げられる。 <Other ingredients>
Other components include, for example, surfactants, thickeners, pigments, leveling agents and the like.
（塗液の製造方法）
本発明の塗液の製造方法は、シロキサン結合を含む疎水性基を有する水溶性ポリマーを合成する工程を含み、混合工程を含むことが好ましく、更に必要に応じてその他の工程を含む。 (Method for producing coating liquid)
The method for producing the coating liquid of the present invention includes a step of synthesizing a water-soluble polymer having a hydrophobic group containing a siloxane bond, preferably includes a mixing step, and further includes other steps as necessary.
本発明の塗液の製造方法は、シロキサン結合を含む疎水性基を有する水溶性ポリマーを合成する工程を含み、混合工程を含むことが好ましく、更に必要に応じてその他の工程を含む。 (Method for producing coating liquid)
The method for producing the coating liquid of the present invention includes a step of synthesizing a water-soluble polymer having a hydrophobic group containing a siloxane bond, preferably includes a mixing step, and further includes other steps as necessary.
シロキサン結合を含む疎水性基を有する水溶性ポリマーは、上述した合成方法により合成することができる。
前記混合工程では、シロキサン結合を含む疎水性基を有する水溶性ポリマー、エアロゲル、及び必要に応じてその他の成分を液状媒体中で混合する。混合方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、シェーキング、磁性スターラー撹拌、機械撹拌、振動撹拌、超音波撹拌などが挙げられる。 A water-soluble polymer having a hydrophobic group containing a siloxane bond can be synthesized by the synthesis method described above.
In the mixing step, the water-soluble polymer having hydrophobic groups containing siloxane bonds, the airgel, and optionally other components are mixed in a liquid medium. The mixing method is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include shaking, magnetic stirrer stirring, mechanical stirring, vibration stirring, and ultrasonic stirring.
前記混合工程では、シロキサン結合を含む疎水性基を有する水溶性ポリマー、エアロゲル、及び必要に応じてその他の成分を液状媒体中で混合する。混合方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、シェーキング、磁性スターラー撹拌、機械撹拌、振動撹拌、超音波撹拌などが挙げられる。 A water-soluble polymer having a hydrophobic group containing a siloxane bond can be synthesized by the synthesis method described above.
In the mixing step, the water-soluble polymer having hydrophobic groups containing siloxane bonds, the airgel, and optionally other components are mixed in a liquid medium. The mixing method is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include shaking, magnetic stirrer stirring, mechanical stirring, vibration stirring, and ultrasonic stirring.
（塗膜）
本発明の塗膜は、シロキサン結合を含む疎水性基を有する水溶性ポリマーと、エアロゲルと、を含有し、更に必要に応じてその他の成分を含有する。
前記塗膜は、上述の本発明の塗液から、液状媒体を除去したものであってよい。即ち、塗膜における各成分としては、上述の塗液における各成分と同じものが例示でき、塗膜における各成分の含有量は、上述の塗液における各成分の固形分含有量と同じであってよい。 (Coating film)
The coating film of the present invention contains a water-soluble polymer having a hydrophobic group containing a siloxane bond, an airgel, and, if necessary, other components.
The coating film may be obtained by removing the liquid medium from the coating liquid of the present invention described above. That is, each component in the coating film can be exemplified by the same components as those in the coating liquid described above, and the content of each component in the coating film is the same as the solid content of each component in the coating liquid described above. you can
本発明の塗膜は、シロキサン結合を含む疎水性基を有する水溶性ポリマーと、エアロゲルと、を含有し、更に必要に応じてその他の成分を含有する。
前記塗膜は、上述の本発明の塗液から、液状媒体を除去したものであってよい。即ち、塗膜における各成分としては、上述の塗液における各成分と同じものが例示でき、塗膜における各成分の含有量は、上述の塗液における各成分の固形分含有量と同じであってよい。 (Coating film)
The coating film of the present invention contains a water-soluble polymer having a hydrophobic group containing a siloxane bond, an airgel, and, if necessary, other components.
The coating film may be obtained by removing the liquid medium from the coating liquid of the present invention described above. That is, each component in the coating film can be exemplified by the same components as those in the coating liquid described above, and the content of each component in the coating film is the same as the solid content of each component in the coating liquid described above. you can
前記塗液を対象物に塗布する方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ディップコート、スプレーコート、スピンコート、ロールコートなどが挙げられる。
The method of applying the coating liquid to the object is not particularly limited and can be appropriately selected according to the purpose. Examples include dip coating, spray coating, spin coating, and roll coating.
前記塗液を塗布する対象物は特に限定されない。前記対象物を構成する材料は、例えば、金属、セラミック、ガラス、樹脂、又はこれらの複合材料等であってよい。また、前記対象物の形態は、使用目的、材質等に応じて適宜選択することができ、例えば、ブロック状、シート状、パウダー状、繊維状などが挙げられる。
The object to which the coating liquid is applied is not particularly limited. The material forming the object may be, for example, metal, ceramic, glass, resin, or a composite material thereof. The form of the object can be appropriately selected depending on the purpose of use, material, etc. Examples thereof include block, sheet, powder, and fibrous forms.
前記塗膜の平均厚さは、特に制限はなく、目的に応じて適宜選択することができるが、０．０１ｍｍ以上３０ｍｍ以下が好ましく、０．１ｍｍ以上２０ｍｍ以下がより好ましい。
The average thickness of the coating film is not particularly limited, and can be appropriately selected according to the purpose.
本発明の塗膜は、粉落ちの発生を防止でき、エアロゲルに由来する優れた断熱性を有しているので、例えば、携帯情報端末、車載バッテリー、車載内装品、極低温容器、宇宙分野、建築分野、自動車分野、家電分野、半導体分野、産業用設備等における断熱材としての用途などに幅広く適用できる。また、前記塗膜は、断熱材としての用途の他に、撥水材、吸音材、静振材、触媒担持材等としても利用することができる。
The coating film of the present invention can prevent the occurrence of powder falling off and has excellent heat insulating properties derived from aerogel. It can be widely applied to the construction field, automobile field, home appliance field, semiconductor field, use as a heat insulating material in industrial equipment, etc. In addition to being used as a heat insulating material, the coating film can also be used as a water repellent material, a sound absorbing material, a vibration damping material, a catalyst supporting material, and the like.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。
Examples of the present invention will be described below, but the present invention is not limited to these examples.
（合成例１）
＜シロキサン結合を含む疎水性基を有するポリビニルアルコール２の合成＞
撹拌子、冷却管、温度計、及び滴下ロートを備えた２００ｍＬの三口フラスコ中に、１０％ポリビニルアルコール水溶液（ポリビニルアルコール１）（商品名：クラレポバール ５－８８、株式会社クラレ製、数平均分子量：約２,４０００）１００ｇ、苛性ソーダ（水酸化ナトリウム、富士フイルム和光純薬株式会社製）０．１ｇ加え、エポキシシリコーン（商品名：Ｘ－２２－１７３ＢＸ、信越化学工業株式会社製）を２ｇ加えて７０℃で５時間撹拌した。反応終了後、中和した後にアセトンにて生成物を析出させ、洗浄後、８０℃で２４時間減圧乾燥を行い、８．３ｇの合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を得た。ＮＭＲを用いた分析により、合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２の疎水化度は０．２質量％であった。 (Synthesis example 1)
<Synthesis of polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond>
A 10% polyvinyl alcohol aqueous solution (polyvinyl alcohol 1) (trade name: Kuraray Poval 5-88, manufactured by Kuraray Co., Ltd., number average molecular weight : about 2,4000), 0.1 g of caustic soda (sodium hydroxide, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) is added, and 2 g of epoxy silicone (trade name: X-22-173BX, manufactured by Shin-Etsu Chemical Co., Ltd.) is added. The mixture was stirred at 70° C. for 5 hours. After the reaction was completed, the product was precipitated with acetone after neutralization, washed, and dried under reduced pressure at 80° C. for 24 hours. got Analysis using NMR revealed that the degree of hydrophobization of polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 1 was 0.2% by mass.
＜シロキサン結合を含む疎水性基を有するポリビニルアルコール２の合成＞
撹拌子、冷却管、温度計、及び滴下ロートを備えた２００ｍＬの三口フラスコ中に、１０％ポリビニルアルコール水溶液（ポリビニルアルコール１）（商品名：クラレポバール ５－８８、株式会社クラレ製、数平均分子量：約２,４０００）１００ｇ、苛性ソーダ（水酸化ナトリウム、富士フイルム和光純薬株式会社製）０．１ｇ加え、エポキシシリコーン（商品名：Ｘ－２２－１７３ＢＸ、信越化学工業株式会社製）を２ｇ加えて７０℃で５時間撹拌した。反応終了後、中和した後にアセトンにて生成物を析出させ、洗浄後、８０℃で２４時間減圧乾燥を行い、８．３ｇの合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を得た。ＮＭＲを用いた分析により、合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２の疎水化度は０．２質量％であった。 (Synthesis example 1)
<Synthesis of polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond>
A 10% polyvinyl alcohol aqueous solution (polyvinyl alcohol 1) (trade name: Kuraray Poval 5-88, manufactured by Kuraray Co., Ltd., number average molecular weight : about 2,4000), 0.1 g of caustic soda (sodium hydroxide, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) is added, and 2 g of epoxy silicone (trade name: X-22-173BX, manufactured by Shin-Etsu Chemical Co., Ltd.) is added. The mixture was stirred at 70° C. for 5 hours. After the reaction was completed, the product was precipitated with acetone after neutralization, washed, and dried under reduced pressure at 80° C. for 24 hours. got Analysis using NMR revealed that the degree of hydrophobization of polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 1 was 0.2% by mass.
（合成例２）
＜シロキサン結合を含む疎水性基を有するセルロース２の合成＞
合成例１において、１０％ポリビニルアルコール水溶液（商品名：クラレポバール ５－８８、株式会社クラレ製）を、セルロース１（商品名：メトローズ ６０ＳＨ－１００００、信越化学工業株式会社製）に代えた以外は、合成例１と同様にして、合成例２のシロキサン結合を含む疎水性基を有するセルロース２を得た。ＮＭＲを用いた分析により、合成例２のシロキサン結合を含む疎水性基を有するセルロース２の疎水化度は０．２質量％であった。 (Synthesis example 2)
<Synthesis of Cellulose 2 Having Hydrophobic Groups Containing Siloxane Bonds>
In Synthesis Example 1, except that the 10% polyvinyl alcohol aqueous solution (trade name: Kuraray Poval 5-88, manufactured by Kuraray Co., Ltd.) was replaced with cellulose 1 (trade name: Metrose 60SH-10000, manufactured by Shin-Etsu Chemical Co., Ltd.) Cellulose 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 2 was obtained in the same manner as in Synthesis Example 1. According to NMR analysis, the hydrophobicity of cellulose 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 2 was 0.2% by mass.
＜シロキサン結合を含む疎水性基を有するセルロース２の合成＞
合成例１において、１０％ポリビニルアルコール水溶液（商品名：クラレポバール ５－８８、株式会社クラレ製）を、セルロース１（商品名：メトローズ ６０ＳＨ－１００００、信越化学工業株式会社製）に代えた以外は、合成例１と同様にして、合成例２のシロキサン結合を含む疎水性基を有するセルロース２を得た。ＮＭＲを用いた分析により、合成例２のシロキサン結合を含む疎水性基を有するセルロース２の疎水化度は０．２質量％であった。 (Synthesis example 2)
<Synthesis of Cellulose 2 Having Hydrophobic Groups Containing Siloxane Bonds>
In Synthesis Example 1, except that the 10% polyvinyl alcohol aqueous solution (trade name: Kuraray Poval 5-88, manufactured by Kuraray Co., Ltd.) was replaced with cellulose 1 (trade name: Metrose 60SH-10000, manufactured by Shin-Etsu Chemical Co., Ltd.) Cellulose 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 2 was obtained in the same manner as in Synthesis Example 1. According to NMR analysis, the hydrophobicity of cellulose 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 2 was 0.2% by mass.
（合成例３）
＜アルキル基（ステアリル基）を有するセルロース３の合成＞
撹拌子、冷却管、温度計、及び滴下ロートを備えた２００ｍＬの三口フラスコ中に、１０％ヒドロキシプロピルメチルセルロース水溶液（商品名：メトローズ ６０ＳＨ－１００００、信越化学工業株式会社製）１００ｇ、及び苛性ソーダ（水酸化ナトリウム、富士フイルム和光純薬株式会社製）０．５ｇ加え、ステアリルグリシジルエーテル（四日市合成株式会社製）を５ｇ加えて７０℃で３時間撹拌後、９０℃に昇温し２時間撹拌した。反応終了後、中和した後に熱水にて生成物を洗浄後、８０℃で２４時間減圧乾燥を行い、９．１ｇのステアリル基を有するヒドロキシプロピルメチルセルロース３を得た。ＮＭＲを用いた分析により、アルキル基（ステアリル基）を有するセルロース３のステアリル基の導入率（疎水化度）は約０．５質量％であることを確認した。 (Synthesis Example 3)
<Synthesis of cellulose 3 having an alkyl group (stearyl group)>
In a 200 mL three-necked flask equipped with a stirrer, condenser, thermometer, and dropping funnel, 100 g of 10% hydroxypropyl methylcellulose aqueous solution (trade name: Metolose 60SH-10000, manufactured by Shin-Etsu Chemical Co., Ltd.), and caustic soda (water 0.5 g of sodium oxide, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added, 5 g of stearyl glycidyl ether (manufactured by Yokkaichi Gosei Co., Ltd.) was added, and the mixture was stirred at 70° C. for 3 hours, then heated to 90° C. and stirred for 2 hours. After completion of the reaction, the product was neutralized, washed with hot water, and dried under reduced pressure at 80° C. for 24 hours to obtain 9.1 g of hydroxypropylmethylcellulose 3 having a stearyl group. Analysis using NMR confirmed that the stearyl group introduction rate (hydrophobicity) of cellulose 3 having an alkyl group (stearyl group) was about 0.5% by mass.
＜アルキル基（ステアリル基）を有するセルロース３の合成＞
撹拌子、冷却管、温度計、及び滴下ロートを備えた２００ｍＬの三口フラスコ中に、１０％ヒドロキシプロピルメチルセルロース水溶液（商品名：メトローズ ６０ＳＨ－１００００、信越化学工業株式会社製）１００ｇ、及び苛性ソーダ（水酸化ナトリウム、富士フイルム和光純薬株式会社製）０．５ｇ加え、ステアリルグリシジルエーテル（四日市合成株式会社製）を５ｇ加えて７０℃で３時間撹拌後、９０℃に昇温し２時間撹拌した。反応終了後、中和した後に熱水にて生成物を洗浄後、８０℃で２４時間減圧乾燥を行い、９．１ｇのステアリル基を有するヒドロキシプロピルメチルセルロース３を得た。ＮＭＲを用いた分析により、アルキル基（ステアリル基）を有するセルロース３のステアリル基の導入率（疎水化度）は約０．５質量％であることを確認した。 (Synthesis Example 3)
<Synthesis of cellulose 3 having an alkyl group (stearyl group)>
In a 200 mL three-necked flask equipped with a stirrer, condenser, thermometer, and dropping funnel, 100 g of 10% hydroxypropyl methylcellulose aqueous solution (trade name: Metolose 60SH-10000, manufactured by Shin-Etsu Chemical Co., Ltd.), and caustic soda (water 0.5 g of sodium oxide, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added, 5 g of stearyl glycidyl ether (manufactured by Yokkaichi Gosei Co., Ltd.) was added, and the mixture was stirred at 70° C. for 3 hours, then heated to 90° C. and stirred for 2 hours. After completion of the reaction, the product was neutralized, washed with hot water, and dried under reduced pressure at 80° C. for 24 hours to obtain 9.1 g of hydroxypropylmethylcellulose 3 having a stearyl group. Analysis using NMR confirmed that the stearyl group introduction rate (hydrophobicity) of cellulose 3 having an alkyl group (stearyl group) was about 0.5% by mass.
（実施例１）
合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を１ｇ、蒸留水２４ｇに溶解し、シリカエアロゲル（商品名：ＭＴ－１１００、キャボット社製）を５ｇ加えて、あわとり練太郎ＡＲ－１００（株式会社シンキー製）を用い、２,０００ｒｐｍで１０分間撹拌し、実施例１の塗液を得た。 (Example 1)
1 g of polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 1 is dissolved in 24 g of distilled water, 5 g of silica airgel (trade name: MT-1100, manufactured by Cabot Corporation) is added, and Awatori Mixer AR is added. -100 (manufactured by Thinky Co., Ltd.) and stirred at 2,000 rpm for 10 minutes to obtain a coating liquid of Example 1.
合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を１ｇ、蒸留水２４ｇに溶解し、シリカエアロゲル（商品名：ＭＴ－１１００、キャボット社製）を５ｇ加えて、あわとり練太郎ＡＲ－１００（株式会社シンキー製）を用い、２,０００ｒｐｍで１０分間撹拌し、実施例１の塗液を得た。 (Example 1)
1 g of polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond of Synthesis Example 1 is dissolved in 24 g of distilled water, 5 g of silica airgel (trade name: MT-1100, manufactured by Cabot Corporation) is added, and Awatori Mixer AR is added. -100 (manufactured by Thinky Co., Ltd.) and stirred at 2,000 rpm for 10 minutes to obtain a coating liquid of Example 1.
（実施例２）
実施例１において、合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を、合成例２のシロキサン結合を含む疎水性基を有するセルロース２に代えた以外は、実施例１と同様にして、実施例２の塗液を得た。 (Example 2)
In Example 1, the procedure was the same as in Example 1 except that the polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was replaced with the cellulose 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 2. Thus, a coating liquid of Example 2 was obtained.
実施例１において、合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を、合成例２のシロキサン結合を含む疎水性基を有するセルロース２に代えた以外は、実施例１と同様にして、実施例２の塗液を得た。 (Example 2)
In Example 1, the procedure was the same as in Example 1 except that the polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was replaced with the cellulose 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 2. Thus, a coating liquid of Example 2 was obtained.
（実施例３）
実施例１において、蒸留水２６ｇ及びシリカエアロゲル（商品名：ＭＴ－１１００、キャボット社製）３ｇに変更した以外は、実施例１と同様にして、実施例３の塗液を得た。 (Example 3)
A coating liquid of Example 3 was obtained in the same manner as in Example 1, except that 26 g of distilled water and 3 g of silica airgel (trade name: MT-1100, manufactured by Cabot Corporation) were used.
実施例１において、蒸留水２６ｇ及びシリカエアロゲル（商品名：ＭＴ－１１００、キャボット社製）３ｇに変更した以外は、実施例１と同様にして、実施例３の塗液を得た。 (Example 3)
A coating liquid of Example 3 was obtained in the same manner as in Example 1, except that 26 g of distilled water and 3 g of silica airgel (trade name: MT-1100, manufactured by Cabot Corporation) were used.
（実施例４）
実施例１において、蒸留水２８ｇ及びシリカエアロゲル（商品名：ＭＴ－１１００、キャボット社製）１ｇに変更した以外は、実施例１と同様にして、実施例４の塗液を得た。 (Example 4)
A coating liquid of Example 4 was obtained in the same manner as in Example 1, except that 28 g of distilled water and 1 g of silica airgel (trade name: MT-1100, manufactured by Cabot Corporation) were used.
実施例１において、蒸留水２８ｇ及びシリカエアロゲル（商品名：ＭＴ－１１００、キャボット社製）１ｇに変更した以外は、実施例１と同様にして、実施例４の塗液を得た。 (Example 4)
A coating liquid of Example 4 was obtained in the same manner as in Example 1, except that 28 g of distilled water and 1 g of silica airgel (trade name: MT-1100, manufactured by Cabot Corporation) were used.
（比較例１）
実施例１において、合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を、１０％ポリビニルアルコール水溶液（ポリビニルアルコール１）（商品名：クラレポバール ５－８８、株式会社クラレ製、数平均分子量：約２,４０００）に代えた以外は、実施例１と同様にして、比較例１の塗液を得た。 (Comparative example 1)
In Example 1, polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was added to a 10% polyvinyl alcohol aqueous solution (polyvinyl alcohol 1) (trade name: Kuraray Poval 5-88, manufactured by Kuraray Co., Ltd., number average A coating liquid of Comparative Example 1 was obtained in the same manner as in Example 1, except that the molecular weight was changed to about 2,4000).
実施例１において、合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を、１０％ポリビニルアルコール水溶液（ポリビニルアルコール１）（商品名：クラレポバール ５－８８、株式会社クラレ製、数平均分子量：約２,４０００）に代えた以外は、実施例１と同様にして、比較例１の塗液を得た。 (Comparative example 1)
In Example 1, polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was added to a 10% polyvinyl alcohol aqueous solution (polyvinyl alcohol 1) (trade name: Kuraray Poval 5-88, manufactured by Kuraray Co., Ltd., number average A coating liquid of Comparative Example 1 was obtained in the same manner as in Example 1, except that the molecular weight was changed to about 2,4000).
（比較例２）
実施例１において、合成例２のシロキサン結合を含む疎水性基を有するセルロース２を、セルロース１（商品名：メトローズ ６０ＳＨ－１００００、信越化学工業株式会社製）に代えた以外は、実施例１と同様にして、比較例２の塗液を得た。 (Comparative example 2)
In Example 1, the cellulose 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 2 was replaced with cellulose 1 (trade name: Metolose 60SH-10000, manufactured by Shin-Etsu Chemical Co., Ltd.). Similarly, a coating liquid of Comparative Example 2 was obtained.
実施例１において、合成例２のシロキサン結合を含む疎水性基を有するセルロース２を、セルロース１（商品名：メトローズ ６０ＳＨ－１００００、信越化学工業株式会社製）に代えた以外は、実施例１と同様にして、比較例２の塗液を得た。 (Comparative example 2)
In Example 1, the cellulose 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 2 was replaced with cellulose 1 (trade name: Metolose 60SH-10000, manufactured by Shin-Etsu Chemical Co., Ltd.). Similarly, a coating liquid of Comparative Example 2 was obtained.
（比較例３）
実施例１において、合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を添加せず、蒸留水を２５ｇとした以外は、実施例１と同様にして、比較例３の塗液を得た。 (Comparative Example 3)
A coating liquid of Comparative Example 3 was prepared in the same manner as in Example 1 except that polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was not added and 25 g of distilled water was used. Obtained.
実施例１において、合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を添加せず、蒸留水を２５ｇとした以外は、実施例１と同様にして、比較例３の塗液を得た。 (Comparative Example 3)
A coating liquid of Comparative Example 3 was prepared in the same manner as in Example 1 except that polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was not added and 25 g of distilled water was used. Obtained.
（比較例４）
実施例１において、合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を、合成例３のアルキル基（ステアリル基）を有するセルロース３に代えた以外は、実施例１と同様にして、比較例４の塗液を得た。
なお、合成例３のアルキル基（ステアリル基）を有するセルロース３は、特開２０２０－１７２５８０号公報の実施例１で用いているサンジェロース９０Ｌ（大同化成工業株式会社製）を再現したものである。大同化成工業株式会社の製品カタログ（http://www.daido-chem.co.jp/topics/view/2、２０２２年２月９日検索）から、サンジェロース９０Ｌのアルキル基（ステアリル基）導入率（疎水化度）は０．３質量％～０．６質量％である。 (Comparative Example 4)
In Example 1, in the same manner as in Example 1, except that the polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was replaced with the cellulose 3 having an alkyl group (stearyl group) in Synthesis Example 3. , to obtain a coating liquid of Comparative Example 4.
The cellulose 3 having an alkyl group (stearyl group) in Synthesis Example 3 is a reproduction of Sangelose 90L (manufactured by Daido Kasei Co., Ltd.) used in Example 1 of JP-A-2020-172580. . Introduction of alkyl group (stearyl group) of Sangelose 90L from the product catalog of Daido Kasei Co., Ltd. (http://www.daido-chem.co.jp/topics/view/2, retrieved on February 9, 2022) The ratio (hydrophobicity) is 0.3% by mass to 0.6% by mass.
実施例１において、合成例１のシロキサン結合を含む疎水性基を有するポリビニルアルコール２を、合成例３のアルキル基（ステアリル基）を有するセルロース３に代えた以外は、実施例１と同様にして、比較例４の塗液を得た。
なお、合成例３のアルキル基（ステアリル基）を有するセルロース３は、特開２０２０－１７２５８０号公報の実施例１で用いているサンジェロース９０Ｌ（大同化成工業株式会社製）を再現したものである。大同化成工業株式会社の製品カタログ（http://www.daido-chem.co.jp/topics/view/2、２０２２年２月９日検索）から、サンジェロース９０Ｌのアルキル基（ステアリル基）導入率（疎水化度）は０．３質量％～０．６質量％である。 (Comparative Example 4)
In Example 1, in the same manner as in Example 1, except that the polyvinyl alcohol 2 having a hydrophobic group containing a siloxane bond in Synthesis Example 1 was replaced with the cellulose 3 having an alkyl group (stearyl group) in Synthesis Example 3. , to obtain a coating liquid of Comparative Example 4.
The cellulose 3 having an alkyl group (stearyl group) in Synthesis Example 3 is a reproduction of Sangelose 90L (manufactured by Daido Kasei Co., Ltd.) used in Example 1 of JP-A-2020-172580. . Introduction of alkyl group (stearyl group) of Sangelose 90L from the product catalog of Daido Kasei Co., Ltd. (http://www.daido-chem.co.jp/topics/view/2, retrieved on February 9, 2022) The ratio (hydrophobicity) is 0.3% by mass to 0.6% by mass.
次に、以下のようにして、諸特性を評価した。結果を表１及び表２に示した。なお、表１及び表２中の各成分の含有量は質量基準である。
Next, we evaluated various characteristics as follows. The results are shown in Tables 1 and 2. In addition, the content of each component in Tables 1 and 2 is based on mass.
＜分散性＞
あわとり練太郎ＡＲ－１００（株式会社シンキー製）を用い、２,０００ｒｐｍで１０分間撹拌直後の分散状態を観察し、以下の基準に基づき、分散性を評価した。なお、Ａ以上が実施可能レベルである。
［評価基準］
Ａ：ダマが無く液状である
Ｂ：液状であるがダマがある
Ｃ：ダマの有無によらず、かさが増え、ホイップ状である
Ｄ：分散しない <Dispersibility>
Using Awatori Mixer AR-100 (manufactured by Thinky Co., Ltd.), the dispersion state was observed immediately after stirring at 2,000 rpm for 10 minutes, and the dispersibility was evaluated based on the following criteria. Note that A or higher is the practicable level.
[Evaluation criteria]
A: Liquid without lumps B: Liquid but with lumps C: Increased volume and whipped shape regardless of presence or absence of lumps D: Does not disperse
あわとり練太郎ＡＲ－１００（株式会社シンキー製）を用い、２,０００ｒｐｍで１０分間撹拌直後の分散状態を観察し、以下の基準に基づき、分散性を評価した。なお、Ａ以上が実施可能レベルである。
［評価基準］
Ａ：ダマが無く液状である
Ｂ：液状であるがダマがある
Ｃ：ダマの有無によらず、かさが増え、ホイップ状である
Ｄ：分散しない <Dispersibility>
Using Awatori Mixer AR-100 (manufactured by Thinky Co., Ltd.), the dispersion state was observed immediately after stirring at 2,000 rpm for 10 minutes, and the dispersibility was evaluated based on the following criteria. Note that A or higher is the practicable level.
[Evaluation criteria]
A: Liquid without lumps B: Liquid but with lumps C: Increased volume and whipped shape regardless of presence or absence of lumps D: Does not disperse
＜粉落ち＞
得られた塗液を１００℃で３時間の条件で乾燥して、３００μｍの厚みとなるようにシート化を行った。得られた各シートの乾燥後のエアロゲルの粉落ちについて、以下の基準で評価した。なお、Ａ以上が実施可能レベルである。
［評価基準］
Ａ：粉落ちが無い
Ｂ：シートに触れると粉落ちが発生する
Ｃ：シートを動かすだけで粉落ちが発生する
Ｄ：シートが形成できない <Powder drop>
The resulting coating liquid was dried at 100° C. for 3 hours to form a sheet having a thickness of 300 μm. The following criteria evaluated the powder fall-off of the airgel after drying of each obtained sheet. Note that A or higher is the practicable level.
[Evaluation criteria]
A: No powder falling off B: Powder falling off when the sheet is touched C: Powder falling off just by moving the sheet D: Sheet cannot be formed
得られた塗液を１００℃で３時間の条件で乾燥して、３００μｍの厚みとなるようにシート化を行った。得られた各シートの乾燥後のエアロゲルの粉落ちについて、以下の基準で評価した。なお、Ａ以上が実施可能レベルである。
［評価基準］
Ａ：粉落ちが無い
Ｂ：シートに触れると粉落ちが発生する
Ｃ：シートを動かすだけで粉落ちが発生する
Ｄ：シートが形成できない <Powder drop>
The resulting coating liquid was dried at 100° C. for 3 hours to form a sheet having a thickness of 300 μm. The following criteria evaluated the powder fall-off of the airgel after drying of each obtained sheet. Note that A or higher is the practicable level.
[Evaluation criteria]
A: No powder falling off B: Powder falling off when the sheet is touched C: Powder falling off just by moving the sheet D: Sheet cannot be formed
＜熱伝導率＞
得られた各塗液を用いて２００ｍｍ×２００ｍｍ×０．３ｍｍのサイズの塗膜を作製し、熱伝導率測定装置（ＨＦＭ－４４６、ＮＥＴＺＳＣＨ社製）を用い、２枚の板（加熱板と冷却板）との間に前記塗膜を挟んで、加熱板加熱時の熱伝導率を測定した。 <Thermal conductivity>
A coating film having a size of 200 mm × 200 mm × 0.3 mm was prepared using each of the obtained coating liquids, and two plates (heating plate and A cooling plate) was sandwiched between the coating film and the thermal conductivity during heating with a hot plate was measured.
得られた各塗液を用いて２００ｍｍ×２００ｍｍ×０．３ｍｍのサイズの塗膜を作製し、熱伝導率測定装置（ＨＦＭ－４４６、ＮＥＴＺＳＣＨ社製）を用い、２枚の板（加熱板と冷却板）との間に前記塗膜を挟んで、加熱板加熱時の熱伝導率を測定した。 <Thermal conductivity>
A coating film having a size of 200 mm × 200 mm × 0.3 mm was prepared using each of the obtained coating liquids, and two plates (heating plate and A cooling plate) was sandwiched between the coating film and the thermal conductivity during heating with a hot plate was measured.
本発明の塗膜は、粉落ちの発生を防止でき、エアロゲルに由来する優れた断熱性を有するので、例えば、携帯情報端末、車載バッテリー、車載内装品、極低温容器、宇宙分野、建築分野、自動車分野、家電分野、半導体分野、産業用設備等における断熱材としての用途などに幅広く適用できる。
The coating film of the present invention can prevent the occurrence of powder falling off and has excellent heat insulation derived from aerogel. It can be widely applied to the automotive field, the home appliance field, the semiconductor field, and the use as a heat insulating material in industrial equipment.
本国際出願は２０２２年２月１４日に出願した日本国特許出願２０２２－０２０１０３号に基づく優先権を主張するものであり、日本国特許出願２０２２－０２０１０３号の全内容を本国際出願に援用する。
This international application claims priority based on Japanese Patent Application No. 2022-020103 filed on February 14, 2022, and the entire contents of Japanese Patent Application No. 2022-020103 are incorporated into this international application. .
Claims (10)
- シロキサン結合を含む疎水性基を有する水溶性ポリマー、エアロゲル、及び液状媒体を含有することを特徴とする塗液。 A coating liquid characterized by containing a water-soluble polymer, an airgel, and a liquid medium having a hydrophobic group containing a siloxane bond.
- 前記シロキサン結合を含む疎水性基が下記一般式（１）及び一般式（２）のいずれかで表される、請求項１に記載の塗液。
- 前記水溶性ポリマーが、ポリビニルアルコール、ポリアクリル酸、セルロース、キトサン、及びアルギン酸から選択される少なくとも１種を含む、請求項１から２のいずれかに記載の塗液。 The coating liquid according to any one of claims 1 and 2, wherein the water-soluble polymer contains at least one selected from polyvinyl alcohol, polyacrylic acid, cellulose, chitosan, and alginic acid.
- 前記シロキサン結合を含む疎水性基を有する水溶性ポリマーの数平均分子量が５,０００以上である、請求項１から３のいずれかに記載の塗液。 The coating liquid according to any one of claims 1 to 3, wherein the water-soluble polymer having a hydrophobic group containing siloxane bonds has a number average molecular weight of 5,000 or more.
- 前記エアロゲルがシリカエアロゲルである、請求項１から４のいずれかに記載の塗液。 The coating liquid according to any one of claims 1 to 4, wherein the airgel is silica airgel.
- 前記エアロゲルの含有量が塗液中の固形分の全質量基準で、５０質量％以上である、請求項１から５のいずれかに記載の塗液。 The coating liquid according to any one of claims 1 to 5, wherein the content of the airgel is 50% by mass or more based on the total mass of solids in the coating liquid.
- 前記シロキサン結合を含む疎水性基を有する水溶性ポリマーの疎水化度が、水溶性ポリマーの水酸基量に対して５質量％以下である、請求項１から６のいずれかに記載の塗液。 The coating liquid according to any one of claims 1 to 6, wherein the water-soluble polymer having a hydrophobic group containing a siloxane bond has a degree of hydrophobicity of 5% by mass or less relative to the amount of hydroxyl groups in the water-soluble polymer.
- 断熱材用である、請求項１から７のいずれかに記載の塗液。 The coating liquid according to any one of claims 1 to 7, which is for heat insulating materials.
- 請求項１から８のいずれかに記載の塗液の製造方法であって、
水溶性ポリマーと下記一般式（３）で表される化合物を反応させてシロキサン結合を含む疎水性基を有する水溶性ポリマーを合成する工程を含むことを特徴とする塗液の製造方法。
A method for producing a coating liquid, comprising the step of reacting a water-soluble polymer with a compound represented by the following general formula (3) to synthesize a water-soluble polymer having a hydrophobic group containing a siloxane bond.
- シロキサン結合を含む疎水性基を有する水溶性ポリマーと、
エアロゲルと、を含有することを特徴とする塗膜。
a water-soluble polymer having a hydrophobic group containing a siloxane bond;
A coating film characterized by containing an aerogel.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-020103 | 2022-02-14 | ||
| JP2022020103A JP2023117508A (en) | 2022-02-14 | 2022-02-14 | Coating liquid, method for producing coating liquid, and coating film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023153252A1 true WO2023153252A1 (en) | 2023-08-17 |
Family
ID=87564194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/002782 WO2023153252A1 (en) | 2022-02-14 | 2023-01-30 | Coating liquid, method for producing coating liquid, and coating film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2023117508A (en) |
| WO (1) | WO2023153252A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5648211A (en) * | 1979-09-26 | 1981-05-01 | Toshiba Silicone Co Ltd | Emulsion composition for anti-foaming |
| CN107337976A (en) * | 2017-08-25 | 2017-11-10 | 安徽智博新材料科技有限公司 | Anti-aging exterior coating of a kind of anticracking and preparation method thereof |
| CN111592813A (en) * | 2020-06-22 | 2020-08-28 | 河南宣和钧釉环保材料有限公司 | Intumescent fire-retardant coating and preparation method thereof |
| CN111592805A (en) * | 2020-06-12 | 2020-08-28 | 中国计量大学 | Coating and preparation method and application thereof |
| JP2020172590A (en) * | 2019-04-10 | 2020-10-22 | 日立化成株式会社 | Coating liquid, composite material and coating film |
| CN113512333A (en) * | 2020-04-10 | 2021-10-19 | 中国石油化工股份有限公司 | Organosilicon modified acrylic acid anticorrosive heat-insulating coating and preparation method and application thereof |
-
2022
- 2022-02-14 JP JP2022020103A patent/JP2023117508A/en active Pending
-
2023
- 2023-01-30 WO PCT/JP2023/002782 patent/WO2023153252A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5648211A (en) * | 1979-09-26 | 1981-05-01 | Toshiba Silicone Co Ltd | Emulsion composition for anti-foaming |
| CN107337976A (en) * | 2017-08-25 | 2017-11-10 | 安徽智博新材料科技有限公司 | Anti-aging exterior coating of a kind of anticracking and preparation method thereof |
| JP2020172590A (en) * | 2019-04-10 | 2020-10-22 | 日立化成株式会社 | Coating liquid, composite material and coating film |
| CN113512333A (en) * | 2020-04-10 | 2021-10-19 | 中国石油化工股份有限公司 | Organosilicon modified acrylic acid anticorrosive heat-insulating coating and preparation method and application thereof |
| CN111592805A (en) * | 2020-06-12 | 2020-08-28 | 中国计量大学 | Coating and preparation method and application thereof |
| CN111592813A (en) * | 2020-06-22 | 2020-08-28 | 河南宣和钧釉环保材料有限公司 | Intumescent fire-retardant coating and preparation method thereof |
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|---|---|
| JP2023117508A (en) | 2023-08-24 |
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