WO2020213486A1 - Corps de structure, élément échangeur de chaleur et élément transporteur - Google Patents

Corps de structure, élément échangeur de chaleur et élément transporteur Download PDF

Info

Publication number
WO2020213486A1
WO2020213486A1 PCT/JP2020/015721 JP2020015721W WO2020213486A1 WO 2020213486 A1 WO2020213486 A1 WO 2020213486A1 JP 2020015721 W JP2020015721 W JP 2020015721W WO 2020213486 A1 WO2020213486 A1 WO 2020213486A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
represented
compound
formula
hydrolyzable
Prior art date
Application number
PCT/JP2020/015721
Other languages
English (en)
Japanese (ja)
Inventor
純平 植野
鈴木　秀也
啓 高野
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Publication of WO2020213486A1 publication Critical patent/WO2020213486A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F17/00—Removing ice or water from heat-exchange apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings

Definitions

  • the present invention relates to a structure, a member for a heat exchanger, and a member for a transport aircraft.
  • Water repellency is evaluated by the size of the contact angle of water, while water repellency is evaluated by the small sliding angle of water, and no correlation is observed between water repellency and water slickness. Even the above-mentioned fluorine-based surface treatment agent having water repellency may not have the desired effect because it does not have water-sliding property.
  • the problem to be solved by the present invention is to provide a structure having both excellent water repellency and water slipperiness.
  • the present invention is a structure having a sliding water-repellent layer on a base material, and the sliding water-repellent layer has a structure represented by the following formula (1) and a structure represented by the following formula (2). It relates to a structure containing one or more selected from the above and a compound having a silyl group having a hydrolyzable group.
  • the structure of the present invention has a sliding water-repellent layer on a base material, and the sliding water-repellent layer is selected from a structure represented by the following formula (1) and a structure represented by the following formula (2). Includes one or more compounds and a compound having a silyl group having a hydrolyzable group.
  • the compound contained in the sliding water-repellent layer has a silyl group having a hydrolyzable group at one end and a specific perfluoropolyether chain at the other end, so that the compound has high water repellency. And high lubricity can be shown at the same time.
  • the base material of the structure of the present invention is not particularly limited, and for example, a base material made of metal (metal base material), a base material made of resin (resin base material), a base material made of glass (glass base material), and the like can be used. Can be used.
  • the metal constituting the metal base material include iron, copper, aluminum, stainless steel, zinc, silver, gold, platinum, and alloys thereof. Of these, aluminum, copper, or alloys thereof are preferable, and aluminum or an aluminum alloy is more preferable.
  • the resin constituting the resin base material examples include polyethylene, polypropylene, polycabonate, polyester, polystyrene, polymethacrylate, polyvinyl chloride, polyethylene alcohol, polyimide, polyamide, polyurethane, epoxy resin, cellulose resin and the like.
  • the glass constituting the glass base material includes inorganic glass; organic glass; alkali-containing glass such as alkali aluminum silicate glass and soda lime glass; non-alkali glass base material such as borosilicate glass; sapphire glass; crystal glass; quartz. Examples include glass.
  • the base material may be subjected to surface treatment such as etching treatment, plasma treatment, ozone treatment and the like.
  • the shape of the base material is not particularly limited, and examples thereof include a flat plate shape and a curved surface shape, and any shape may be used depending on the intended use.
  • the thickness thereof is not particularly limited, but is, for example, 10 ⁇ m to 1000 ⁇ m, preferably 50 ⁇ m to 500 ⁇ m.
  • the sliding water-repellent layer contains one or more selected from the structure represented by the following formula (1) and the structure represented by the following formula (2), and a compound having a silyl group having a hydrolyzable group. ..
  • the repeating unit contains a 1-perfluoropropyl ether structure.
  • the 1-perfluoropropyl ether structure By including the 1-perfluoropropyl ether structure in the repeating unit, three CF groups are densely arranged on the surface of the sliding water-repellent layer (air interface), and the structure of the present invention has both high water repellency and high water repellency at the same time. It is speculated that it can be shown.
  • the repeating unit contains an n-perfluoroethyl ether structure.
  • the crystallization of the perfluoropoethyl ethers causes the three CF groups at the ends to be oriented toward the surface of the sliding water-repellent layer (air interface). It is speculated that the structure can exhibit both high water repellency and high slipperiness at the same time.
  • the number of repetitions of r is not particularly limited, and is preferably 5 to 100 on average, more preferably 8 to 80 on average, and even more preferably 10 to 60 on average.
  • the number of repetitions of r is not particularly limited, and is preferably 5 to 100 on average, and more preferably 5 to 50 on average.
  • the silyl group having a hydrolyzable group is preferably a silyl group represented by Si (A) 3 (the three A's are independently hydrolyzable or non-hydrolyzable groups, respectively, and the three A's. At least one of them is a hydrolyzable group).
  • the number of hydrolyzable groups in the silyl group represented by Si (A) 3 is at least one, and two or more hydrolyzable groups are preferable because a film having more excellent durability can be formed, and all three are preferable. Is more preferably a hydrolyzable group.
  • the two or more hydrolyzable groups may be the same or different from each other.
  • At least one silyl group represented by Si (A) 3 may have a hydrolyzable group.
  • the two or more non-hydrolyzable groups may be the same or different from each other.
  • hydrolyzable group examples include an alkoxy group such as a methoxy group, an ethoxy group and a propoxy group; an alkoxy group substituted alkoxy group such as a methoxyethoxy group; an acyloxy group such as an acetoxy group, a propionyloxy group and a benzoyloxy group; Alkoxyoxy groups such as propenyloxy group and isobutenyloxy group; imineoxy groups such as dimethylketoxim group, methylethylketoxim group, diethylketoxim group, cyclohexaneoxym group; methylamino group, ethylamino group, dimethylamino group, diethylamino Substituent amino groups such as groups; amide groups such as N-methylacetamide group and N-ethylamide group; substituted aminooxy groups such as dimethylaminooxy group and diethylaminooxy group; halogens such as chlorine and the like
  • an alkoxy group is preferable because the hydrolysis rate is high and a film having excellent durability can be formed quickly, and an alkoxy group having 1 to 6 carbon atoms is more preferable, and the number of carbon atoms is more preferable. 1 to 3 alkoxy groups are more preferable, methoxy groups and ethoxy groups are particularly preferable, and methoxy groups are most preferable.
  • non-hydrolyzable group examples include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. And so on.
  • an alkyl group having 1 to 3 carbon atoms is preferable because it can avoid steric hindrance and increase the hydrolysis rate, and as a result, a film having excellent durability can be formed quickly.
  • Methyl groups are more preferred.
  • a compound having one or more selected from the structure represented by the formula (1) and the structure represented by the formula (2) and a silyl group having a hydrolyzable group is represented by the formula (1).
  • the compound containing the structure represented by the formula (1) is preferably represented by the following formulas (1-1), (1-2), (1-3) or (1-4). It is a compound.
  • R 1 is an alkylene group having 1 to 6 carbon atoms.
  • R 3 is a divalent linking group.
  • Z is a trivalent linking group.
  • Each of B is an organic group or a silyl group represented by Si (A) 3 , and at least one of the two Bs is a silyl group represented by Si (A) 3 .
  • the three A of the silyl group represented by Si (A) 3 are independently hydrolyzable or non-hydrolyzable groups, and at least one of the three A is a hydrolyzable group. .. )
  • the organic group when B is an organic group, the organic group includes, for example, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkenyl group. Phenyl group and the like.
  • the organic group of B is a substituted alkyl group
  • examples of the substituted alkyl group include a partially fluorinated alkyl group having 1 to 6 carbon atoms and a perfluoroalkyl group having 1 to 6 carbon atoms.
  • R 32 is an alkylene group having 1 to 3 carbon atoms.
  • R 33 is a direct bond or an alkylene group having 1 to 6 carbon atoms.
  • R 34 is an alkylene group having 1 to 5 carbon atoms
  • linking group represented by the formula (R 3 -1) include the following.
  • linking group represented by the formula (R 3 -2) include the following.
  • the trivalent linking group of Z in the formulas (1-2) and (1-4) is, for example, a trivalent aliphatic ring group having 4 to 8 carbon atoms, preferably a cyclohexyl group.
  • a is an integer of 1 to 6.
  • a compound having one or more selected from the structure represented by the formula (1) and the structure represented by the formula (2) and a silyl group having a hydrolyzable group is represented by the formula (2).
  • the compound containing the structure represented by the formula (2) is preferably a compound represented by the following formulas (2-1), (2-2) or (2-3).
  • R 1 is an alkylene group having 1 to 6 carbon atoms.
  • R 2 is an alkylene aminoalkylene group or an alkylene thioalkylene group.
  • the three A of the silyl group represented by Si (A) 3 are independently hydrolyzable or non-hydrolyzable groups, and at least one of the three A is a hydrolyzable group. .. )
  • the alkylene group having 1 to 6 carbon atoms of R 1 is preferably an alkylene group having 3 carbon atoms.
  • the alkyleneaminoalkylene group of R 2 is a group in which two alkylene groups are linked by an amino bond (-NH-), and is an alkylenethio.
  • An alkylene group is a group in which two alkylene groups are linked by a thio bond (—S—).
  • the alkylene groups of the alkyleneaminoalkylene group and the alkylenethioalkylene group are independently alkylene groups having 1 to 6 carbon atoms.
  • the method for producing a compound having one or more selected from the structure represented by the formula (1) and the structure represented by the formula (2) and a silyl group having a hydrolyzable group is not particularly limited and is known. It can be manufactured by the method of.
  • the method for producing the compound represented by the formulas (1-1), (1-2), (1-3) or (1-4) is, for example, the carboxylic acid represented by the following formula ( ⁇ -1) and the following formula ( ⁇ -2) or the following formula ( ⁇ ).
  • the second step of reacting with the isocyanate compound represented by -4) is included.
  • R 3 is a divalent linking group.
  • the three A of the silyl groups represented by Si (A) 3 are independently hydrolyzable or non-hydrolyzable groups, and at least one of the three A is a hydrolyzable group.
  • R 1 is an alkylene group having 1 to 6 carbon atoms.
  • the three A of the silyl groups represented by Si (A) 3 are independently hydrolyzable or non-hydrolyzable groups, and at least one of the three A is a hydrolyzable group.
  • R 3 is a divalent linking group.
  • G is an organic group.
  • the first step may be included, and the second step can be omitted.
  • R 1 is an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an n-propylene group).
  • the method for producing the compound represented by the formulas (1-1), (1-2), (1-3) or (1-4) may be carried out in the presence of an organic solvent, if necessary.
  • the organic solvent is not particularly limited as long as it can dissolve the above-mentioned compound group as a raw material.
  • a solvent such as acetone, methyl ethyl ketone, toluene, xylene, etc., which does not have reactivity with an isocyanate group, or a fluorine-based solvent is used.
  • An organic solvent can be used.
  • fluorine-based solvent examples include fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis (trifluoromethyl) benzene and trifluorotoluene; and having 3 to 3 carbon atoms such as perfluorohexane and perfluoromethylcyclohexane. Twelve perfluorocarbon solvents; 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,4,4,5,5,6 Hydrofluorocarbon solvent such as 6-tridecafluorooctane; C 3 F 7 OCH 3 , C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , C 2 F 5 CF (OCH 3 ) C 3 F 7 etc.
  • fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis (trifluoromethyl) benzene and trifluorotoluene; and having 3 to 3 carbon atoms such as perfluorohexane and perfluoromethylcyclohe
  • Hydrofluoroether-based solvent Perfluoropolyether-based solvent such as Fomblin, Garden (manufactured by Solvay), Demnum (manufactured by Daikin Industries), Kleitox (manufactured by Chemers) and the like can be preferably exemplified.
  • the reaction ratio between the compound ( ⁇ -1) and the compound ( ⁇ -2) or the compound ( ⁇ -3) is the carboxyl group of the compound ( ⁇ -1) and the compound ( ⁇ -2) or
  • the ratio of the equivalent ratio (carboxyl group / epoxy group) of the compound ( ⁇ -3) to the epoxy group is preferably 0.5 to 1.5, more preferably 0.9 to 1.1. A ratio of 0.98 to 1.02 is more preferable.
  • the reaction temperature in the first step is not particularly limited, and is usually 50 to 150 ° C.
  • the reaction time is also not particularly limited, and is usually 1 to 10 hours.
  • the reaction ratio between the reactant having a secondary hydroxyl group derived from the epoxy group obtained in the first step and the compound ( ⁇ -4) is the hydroxyl group and the compound ( ⁇ -4) contained in the reactant.
  • the ratio of the equivalent ratio (hydroxyl group / isocyanate group) to the isocyanate group of the is preferably 0.5 to 1.5, more preferably 0.9 to 1.1, and 0.98 to 1.02. Is more preferable.
  • the reaction temperature in the second step is not particularly limited, and is usually 30 to 120 ° C.
  • the reaction time is also not particularly limited, and is usually 1 to 10 hours.
  • the method for producing the compound represented by the formula (2-1), (2-2) or (2-3) is the formula (1-1), (1-2), (1-3) or (1-1).
  • a method similar to the method for producing the compound represented by 4) can be adopted.
  • an alcohol represented by the following formula ( ⁇ -1) with an isocyanate compound represented by the above formula ( ⁇ -4), the formula (2-1), (2-2) or (2)
  • the compound represented by -3) can be produced.
  • the reaction conditions and other raw materials the same reaction conditions and other raw materials as the method for producing the compound represented by the above formulas (1-1), (1-2), (1-3) or (1-4) It is good to adopt.
  • One kind of compound having one or more selected from the structure represented by the formula (1) and the structure represented by the formula (2) in the sliding water-repellent layer and a silyl group having a hydrolyzable group is one kind. It may be used alone or in combination of two or more.
  • the sliding water-repellent layer may include one or more selected from the structure represented by the formula (1) and the structure represented by the formula (2), and a compound having a silyl group having a hydrolyzable group.
  • Other components may be contained as long as the effects of the present invention are not impaired. Examples of the other components include inorganic metal compounds such as inorganic tin compounds, inorganic titanium compounds and inorganic zinc compounds, hydrolysis accelerators such as amine compounds, and storage stabilizers such as alcohol.
  • the sliding water-repellent layer includes one or more selected from the structure represented by the formula (1) and the structure represented by the formula (2), a compound having a silyl group having a hydrolyzable group, and others. It may or may not contain the component of.
  • the sliding water-repellent layer is substantially composed of a compound having one or more selected from the structure represented by the formula (1) and the structure represented by the formula (2) and a silyl group having a hydrolyzable group. At this time, the sliding water-repellent layer may contain unavoidable impurities.
  • the thickness of the sliding water-repellent layer is, for example, 1 to 100 nm, preferably 1 to 50 nm, and more preferably 1 to 20 nm.
  • the structure of the present invention comprises, for example, one or more selected from the structure represented by the formula (1) and the structure represented by the formula (2) on the base material, and a silyl group having a hydrolyzable group. It is produced by applying a solution of a compound having a compound (hereinafter, a compound having this structure may be referred to as a “sliding water-repellent layer compound”), or by immersing a base material in a solution of a sliding water-repellent layer compound. be able to.
  • the cleaning solution include water, ethanol, isopropanol, an aqueous solution of sodium hydroxide, an aqueous solution of tetramethylammonium hydroxide, and a mixed solution thereof.
  • a cleaning liquid By cleaning the base material with a cleaning liquid, dirt such as oil on the surface of the base material can be removed, and the water-repellent sliding layer can be smoothly formed.
  • the surface of the base material may be hydrophilized by performing plasma treatment, UV ozone treatment, or the like.
  • the solvent of the solution of the sliding water-repellent layer compound is not particularly limited as long as it is a solvent capable of dissolving the sliding water-repellent layer compound, and for example, the above formulas (1-1), (1-2) and (1-3). Alternatively, the solvent used in the preparation of the compound represented by (1-4) may be used.
  • the concentration of the sliding water-repellent layer compound is, for example, 0.01% by mass to 30% by mass, preferably 0.01% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass. is there.
  • a compound having one or more selected from the structure represented by the formula (1) and the structure represented by the formula (2) and a silyl group having a hydrolyzable group is a silyl group having a hydrolyzable group.
  • the solution of the sliding water repellent layer compound may not contain, for example, a binder, since can be directly bonded to the substrate.
  • a water-repellent sliding layer can be formed on the base material by drying the base material coated with the solution of the sliding water-repellent layer compound or the base material immersed in the solution of the sliding water-repellent layer compound.
  • the drying temperature is preferably 40 to 200 ° C.
  • the drying time is preferably 5 to 60 minutes.
  • the structure of the present invention can exhibit both water repellency and water sliding property at the same time, the sliding angle of water on the surface of the sliding water repellent layer can be set to 15 ° or less, and the contact of water on the surface of the sliding water repellent layer. The angle can be 110 ° or more. Since the structure of the present invention can exhibit both water repellency and water sliding property at the same time, for example, if the base material is an aluminum base material, the structure of the present invention can be used as a member for a heat exchanger, and the base material can be used. Condensation water and / or frost can be suppressed from adhering to the surface, and high heat exchange efficiency of the heat exchanger can be realized.
  • the structure of the present invention can be used as a member for a transport aircraft, and high visibility stability of the transport aircraft can be realized without water droplets adhering to the glass surface. it can.
  • the sliding angle and the contact angle are each evaluated by the methods described in the examples.
  • r is the number of repetitions, which is 43 on average.
  • the reaction solution was diluted by adding hydrofluoroether so that the concentration of the solvent was 80% by mass.
  • the diluted reaction solution was filtered and purified using a polytetrafluoroethylene (PTFE) filter having a pore size of 1 ⁇ m to obtain a hydrofluoroether solution containing a poly (perfluoroalkylene ether) chain-containing silane compound (1a).
  • PTFE polytetrafluoroethylene
  • Synthesis example 2 In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 36.67 g of 1,3-bis (trifluoromethyl) benzene as a solvent and a carboxylic acid represented by the following formula (Krytox 157FS (L) manufactured by Chemers) )) 50 g, 5.01 g of ⁇ -glycidoxypropyltrimethoxysilane, and 0.165 g of triphenylphosphine as a reaction catalyst were added, stirring was started under a nitrogen stream, and after heating to 105 ° C., about 5 Reacted for time.
  • r is the number of repetitions, which is 13 on average.
  • the reaction solution was diluted by adding hydrofluoroether so that the concentration of the solvent was 80% by mass.
  • the diluted reaction solution was filtered and purified using a polytetrafluoroethylene (PTFE) filter having a pore size of 0.2 ⁇ m to obtain a hydrofluoroether solution containing a poly (perfluoroalkylene ether) chain-containing silane compound (2a). ..
  • PTFE polytetrafluoroethylene
  • Synthesis example 3 In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 40.0 g of alcohol having a poly (perfluoroalkylene ether) chain represented by the following formula and hydrofluoro ether (C 4 F 9 OC) as a solvent and 2 H 5) 43.77g, tin octoate 0.004g added as a urethane catalyst, stirring was started under a stream of nitrogen. After starting stirring, 3.77 g of 3-isocyanatopropyltrimethoxysilane was added dropwise to the reaction solution over 15 minutes while maintaining the temperature at 50 ° C. After completion of the dropping, the alcohol was reacted with 3-isocyanatopropyltrimethoxysilane by stirring at 50 ° C. for 6 hours to obtain a reaction product.
  • r is the number of repetitions, which is 13 on average.
  • the obtained reaction product was subjected to IR spectrum measurement, and it was confirmed that the isocyanate group had disappeared in the reaction product, and it was confirmed that the following compound (3a) was obtained.
  • the reaction solution was diluted by adding hydrofluoroether so that the concentration of the solvent was 80% by mass.
  • the diluted reaction solution was filtered and purified using a polytetrafluoroethylene (PTFE) filter having a pore size of 0.2 ⁇ m to obtain a hydrofluoroether solution containing a poly (perfluoroalkylene ether) chain-containing silane compound (3a). ..
  • PTFE polytetrafluoroethylene
  • r is the number of repetitions, which is 13 on average.
  • Comparative synthesis example 1 In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 45.3 g of a diol having a poly (perfluoroalkylene ether) chain represented by the following formula (1') and tin octylate as a urethanization catalyst. 0.025 g was charged, stirring was started under a nitrogen stream, and 4.7 g of 3-isocyanatopropyltrimethoxysilane was added dropwise over 15 minutes while maintaining 60 ° C. After completion of the dropping, the mixture was stirred at 60 ° C. for 1 hour, then further heated to 80 ° C. and stirred for 2 hours to react the diol with 3-isocyanatopropyltrimethoxysilane to obtain a reaction product.
  • a diol having a poly (perfluoroalkylene ether) chain represented by the following formula (1') and tin octylate as a
  • n is the number of repetitions.
  • Each of the plurality of Xs is independently a perfluoromethylene group or a perfluoroethylene group, and each compound represented by the formula (1') has an average of 21 perfluoromethylene groups and an average of 21 perfluoroethylene groups. It is present and has an average of 126 fluorine atoms.
  • the obtained reaction product was subjected to IR spectrum measurement, and it was confirmed that the isocyanate group had disappeared in the reaction product, and it was confirmed that the following compound (1'a) was obtained.
  • the reaction solution was diluted by adding hydrofluoroether so that the concentration of the solvent was 80% by mass.
  • the diluted reaction solution is filtered and purified using a polytetrafluoroethylene (PTFE) filter having a pore size of 0.2 ⁇ m, and a hydrofluoroether solution containing a poly (perfluoroalkylene ether) chain-containing silane compound (1'a) is prepared. Obtained.
  • PTFE polytetrafluoroethylene
  • PFPE corresponds to-(XO-) n -X-of the above formula (1').
  • Comparative synthesis example 2 55.79 g of diol having a poly (perfluoroalkylene ether) chain represented by the following formula (2') and hydrofluoro ether (C 4 F) in a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device.
  • 9 OC 2 H 5 ) 40 g and 0.03 g of tin octylate as a urethanization catalyst were charged, stirring was started under a nitrogen stream, and 4.12 g of 3-isocyanatopropyltrimethoxysilane was applied for 15 minutes while maintaining 50 ° C. And dropped. After completion of the dropping, the diol was reacted with 3-isocyanatopropyltrimethoxysilane by stirring at 50 ° C. for 6 hours to obtain a reaction product.
  • n is the number of repetitions.
  • the plurality of Xs are independently perfluoromethylene groups or perfluoroethylene groups, and each compound represented by the formula (2') has an average of 30 perfluoromethylene groups and an average of 30 perfluoroethylene groups. It is present and has an average number of fluorine atoms of 180. )
  • the obtained reaction product was subjected to IR spectrum measurement, and it was confirmed that the isocyanate group had disappeared in the reaction product, and it was confirmed that the following compound (2'a) was obtained.
  • the reaction solution was diluted by adding hydrofluoroether so that the concentration of the solvent was 80% by mass.
  • the diluted reaction solution is filtered and purified using a polytetrafluoroethylene (PTFE) filter having a pore size of 0.2 ⁇ m, and a hydrofluoroether solution containing a poly (perfluoroalkylene ether) chain-containing silane compound (2'a) is prepared. Obtained.
  • PTFE polytetrafluoroethylene
  • PFPE corresponds to-(XO-) n -X-of the above formula (2').
  • Comparative synthesis example 3 In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 20 g of alcohol having a poly (perfluoroalkylene ether) chain represented by the following formula (3') and hydrofluoro ether (C 4 F 9 OC). 2 H 5) g of tin octylate 0.006g as 20g and urethanization catalyst, stirring in a nitrogen stream to begin, dropwise over while maintaining 50 ° C. 3- isocyanatoethyl trimethoxysilane 1.31 g 15 min did. After completion of the dropping, the alcohol was reacted with 3-isocyanatopropyltrimethoxysilane by stirring at 50 ° C. for 6 hours to obtain a reaction product.
  • a poly (perfluoroalkylene ether) chain represented by the following formula (3') and hydrofluoro ether (C 4 F 9 OC). 2 H 5
  • the obtained reaction product was subjected to IR spectrum measurement, and it was confirmed that the isocyanate group had disappeared in the reaction product, and it was confirmed that the following compound (3'a) was obtained.
  • the reaction solution was diluted by adding hydrofluoroether so that the concentration of the solvent was 80% by mass.
  • the diluted reaction solution is filtered and purified using a polytetrafluoroethylene (PTFE) filter having a pore size of 0.2 ⁇ m, and a hydrofluoroether solution containing a poly (perfluoroalkylene ether) chain-containing silane compound (3'a) is prepared. Obtained.
  • PTFE polytetrafluoroethylene
  • Comparative synthesis example 4 50 g of trifluoroethanol, 157.99 g of hydrofluoroether (C 4 F 9 OC 2 H 5 ) and 0.047 g of tin octylate as a urethanization catalyst are placed in a glass flask equipped with a stirrer, a thermometer, a cooling tube and a dropping device. The mixture was charged, stirring was started under a nitrogen stream, and 107.99 g of 3-isocyanatopropyltrimethoxysilane was added dropwise over 15 minutes while maintaining 50 ° C. After completion of the dropping, the alcohol was reacted with 3-isocyanatopropyltrimethoxysilane by stirring at 50 ° C. for 6 hours to obtain a reaction product.
  • the obtained reaction product was subjected to IR spectrum measurement, and it was confirmed that the isocyanate group had disappeared in the reaction product, and it was confirmed that the perfluoroalkyl group-containing silane compound (4'a) was obtained.
  • the reaction solution was diluted by adding hydrofluoroether so that the concentration of the solvent was 80% by mass.
  • the diluted reaction solution was filtered and purified using a filter made of polytetrafluoroethylene (PTFE) having a pore size of 0.2 ⁇ m to obtain a hydrofluoroether solution containing a perfluoroalkyl group-containing silane compound (4'a).
  • PTFE polytetrafluoroethylene
  • Comparative synthesis example 5 25 g of 2- (perfluorohexyl) ethanol, 39.98 g of hydrofluoroether (C 4 F 9 OC 2 H 5 ) and octyl as a urethanization catalyst in a glass flask equipped with a stirrer, thermometer, condenser and dropping device. 0.01 g of tin acid acid was charged, stirring was started under a nitrogen stream, and 14.98 g of 3-isocyanatopropyltrimethoxysilane was added dropwise over 15 minutes while maintaining 50 ° C. After completion of the dropping, the alcohol was reacted with 3-isocyanatopropyltrimethoxysilane by stirring at 50 ° C. for 6 hours to obtain a reaction product.
  • the obtained reaction product was subjected to IR spectrum measurement, and it was confirmed that the isocyanate group had disappeared in the reaction product, and it was confirmed that the perfluoroalkyl group-containing silane compound (5'a) was obtained.
  • the reaction solution was diluted by adding hydrofluoroether so that the concentration of the solvent was 80% by mass.
  • the diluted reaction solution was filtered and purified using a filter made of polytetrafluoroethylene (PTFE) having a pore size of 0.2 ⁇ m to obtain a hydrofluoroether solution containing a perfluoroalkyl group-containing silane compound (5'a).
  • PTFE polytetrafluoroethylene
  • Example 1 Hydrofluoroether was further added to the solution of compound (1a) prepared in Synthesis Example 1 to prepare a coating solution of 0.1% by weight of compound (1a).
  • the pretreated glass plate was immersed in the obtained coating liquid and allowed to stand for 1 hour. After standing, the glass plate was taken out and dried at 150 ° C. for 30 minutes to produce a coated plate (base material: glass plate) which is a laminate in which a layer containing the compound (1a) is laminated on the base material.
  • the pretreatment of the glass plate is a process in which a 7 cm ⁇ 7 cm glass plate is passed through a plasma irradiator and plasma is irradiated until the water contact angle (6 ⁇ l) is measured to be 10 ° or less. The measurement of the water contact angle will be described later.
  • the pretreated aluminum plate was immersed in the obtained coating liquid and allowed to stand for 1 hour. After standing, the aluminum plate was taken out and dried at 150 ° C. for 30 minutes to produce a coated plate (base material: aluminum plate) which is a laminated body in which a layer containing the compound (1a) is laminated on the base material.
  • the pretreatment of the aluminum plate was carried out by immersing a 2.5 cm ⁇ 7.5 cm aluminum flat plate in a 0.5 wt% sodium hydroxide aqueous solution for 5 minutes and then washing with water and methanol.
  • the contact angle and the sliding angle of the two coated plates produced were evaluated by the following methods. The results are shown in Table 1.
  • Contact angle measurement Using a contact angle / sliding angle measuring device (DM-500 manufactured by Kyowa Interface Science Co., Ltd.), 6 ⁇ L of water droplets were dropped onto the layer of compound (1a) on the coating plate, and the contact angles of the water droplets were measured. The contact angle was measured 5 times, and the average value of the 5 times was taken as the contact angle of the coated plate.
  • sliding angle measurement Using a contact angle / sliding angle measuring device (DM-500 manufactured by Kyowa Interface Science Co., Ltd.), 50 ⁇ L of water droplets were dropped onto the layer of compound (1a) on the coating plate, and the stage was tilted at a speed of 2 degrees / second. The angle at which the water droplets started to move was taken as the value of the sliding angle. The measurement was performed 5 times, and the average value of the 5 times was taken as the sliding angle of the coated plate.
  • DM-500 manufactured by Kyowa Interface Science Co., Ltd.
  • Example 2-3 and Comparative Example 1-5 A coated plate was produced and evaluated in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of the compound (1a). The results are shown in Table 1.
  • the coated plate of Example 1-3 can show not only water repellency but also water sliding property at the same time regardless of the material of the base material, as compared with the coated plate of Comparative Example 1-5. You can see that there is.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

L'invention concerne un corps de structure qui est excellent en termes de propriétés d'hydrophobie et de glissement de l'eau. Plus précisément, le corps de structure est un corps de structure comportant une couche de glissement d'eau et hydrophobe sur un matériau de base, la couche de glissement d'eau et hydrophobe contenant un composé comprenant une ou plusieurs structure(s) choisie(s) parmi la structure représentée par la formule (1) et la structure représentée par la formule (2), et un groupe silyle comprenant un groupe hydrolytique.
PCT/JP2020/015721 2019-04-18 2020-04-07 Corps de structure, élément échangeur de chaleur et élément transporteur WO2020213486A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-079289 2019-04-18
JP2019079289 2019-04-18

Publications (1)

Publication Number Publication Date
WO2020213486A1 true WO2020213486A1 (fr) 2020-10-22

Family

ID=72837441

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/015721 WO2020213486A1 (fr) 2019-04-18 2020-04-07 Corps de structure, élément échangeur de chaleur et élément transporteur

Country Status (1)

Country Link
WO (1) WO2020213486A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023032817A1 (fr) * 2021-09-02 2023-03-09 ダイキン工業株式会社 Agent de traitement de surface

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000327772A (ja) * 1999-05-20 2000-11-28 Shin Etsu Chem Co Ltd パーフルオロポリエーテル変性アミノシラン及び表面処理剤並びに該アミノシランの被膜が形成された物品
WO2009008380A1 (fr) * 2007-07-06 2009-01-15 Asahi Glass Company, Limited Agent de traitement de surface, article et nouveau composé éther contenant du fluor
JP2009144133A (ja) * 2007-12-13 2009-07-02 Korea Inst Of Chemical Technology パーフルオロポリエーテル変性シラン化合物、これを含有する防汚性コーティング剤組成物およびこれを適用した膜
JP2015503001A (ja) * 2011-11-15 2015-01-29 スリーエム イノベイティブ プロパティズ カンパニー 潤滑性添加剤を含むフッ素化コーティング
WO2015087902A1 (fr) * 2013-12-13 2015-06-18 旭硝子株式会社 Composition d'éther contenant du fluor, procédé pour sa production, liquide de revêtement, matériau de base présentant une couche de traitement de surface et procédé pour sa production
JP2017014452A (ja) * 2015-07-06 2017-01-19 Dic株式会社 表面改質剤、コーティング組成物及び物品
JP2017031347A (ja) * 2015-08-04 2017-02-09 Dic株式会社 コーティング組成物及び物品
JP2017186495A (ja) * 2016-03-31 2017-10-12 大日本印刷株式会社 難着霜性、難結露性、難着氷性を有する低温環境用部材
JP2019044158A (ja) * 2017-08-31 2019-03-22 Ａｇｃ株式会社 含フッ素エーテル化合物、含フッ素エーテル組成物、コーティング液、物品およびその製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000327772A (ja) * 1999-05-20 2000-11-28 Shin Etsu Chem Co Ltd パーフルオロポリエーテル変性アミノシラン及び表面処理剤並びに該アミノシランの被膜が形成された物品
WO2009008380A1 (fr) * 2007-07-06 2009-01-15 Asahi Glass Company, Limited Agent de traitement de surface, article et nouveau composé éther contenant du fluor
JP2009144133A (ja) * 2007-12-13 2009-07-02 Korea Inst Of Chemical Technology パーフルオロポリエーテル変性シラン化合物、これを含有する防汚性コーティング剤組成物およびこれを適用した膜
JP2015503001A (ja) * 2011-11-15 2015-01-29 スリーエム イノベイティブ プロパティズ カンパニー 潤滑性添加剤を含むフッ素化コーティング
WO2015087902A1 (fr) * 2013-12-13 2015-06-18 旭硝子株式会社 Composition d'éther contenant du fluor, procédé pour sa production, liquide de revêtement, matériau de base présentant une couche de traitement de surface et procédé pour sa production
JP2017014452A (ja) * 2015-07-06 2017-01-19 Dic株式会社 表面改質剤、コーティング組成物及び物品
JP2017031347A (ja) * 2015-08-04 2017-02-09 Dic株式会社 コーティング組成物及び物品
JP2017186495A (ja) * 2016-03-31 2017-10-12 大日本印刷株式会社 難着霜性、難結露性、難着氷性を有する低温環境用部材
JP2019044158A (ja) * 2017-08-31 2019-03-22 Ａｇｃ株式会社 含フッ素エーテル化合物、含フッ素エーテル組成物、コーティング液、物品およびその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023032817A1 (fr) * 2021-09-02 2023-03-09 ダイキン工業株式会社 Agent de traitement de surface
JP2023036547A (ja) * 2021-09-02 2023-03-14 ダイキン工業株式会社 表面処理剤
JP7273352B2 (ja) 2021-09-02 2023-05-15 ダイキン工業株式会社 表面処理剤

Similar Documents

Publication Publication Date Title
JP6044701B2 (ja) 蒸着用フッ素系表面処理剤の硬化被膜を有する物品
KR100940086B1 (ko) 과불소 폴리에테르 변성 실란 화합물과 이를 함유한 방오성 코팅제 조성물 및 이를 적용한 막
JP6248858B2 (ja) フッ素系表面処理剤及び該表面処理剤で表面処理された物品
JP5938280B2 (ja) パーフルオロポリエーテル変性シラン化合物、防汚性被膜形成用組成物、防汚性被膜、およびこの被膜を有する物品
JP6119656B2 (ja) フルオロポリエーテル基含有ポリマー
KR102561500B1 (ko) 표면 처리제
KR102084270B1 (ko) 플루오로옥시알킬렌기 함유 중합체 변성 실란 및 상기 실란을 포함하는 표면 처리제, 및 상기 표면 처리제로 표면 처리된 물품
JP5747699B2 (ja) フルオロオキシアルキレン基含有ポリマー変性シラン及び該シランを含む表面処理剤並びに該表面処理剤で表面処理された物品
TW201736537A (zh) 塗覆劑組成物
CN109071935B (zh) 组合物
WO2017141707A1 (fr) Silane modifié par polymère contenant un groupe fluoropolyéther, agent de traitement de surface et article
JP7392667B2 (ja) 含フッ素エーテル組成物、コーティング液、物品およびその製造方法
US8119765B2 (en) Crosslinkable fluorine-containing ether compound
WO2020213486A1 (fr) Corps de structure, élément échangeur de chaleur et élément transporteur
WO2020246301A1 (fr) Polymère contenant un groupe fluoropolyéther et son procédé de production
WO2006049020A1 (fr) Préparation pour le traitement d’un substrat de verre
WO2020213485A1 (fr) Corps de structure, procédé de production de corps de structure, élément d'échangeur de chaleur et échangeur de chaleur
JP2014156061A (ja) 下地層及び撥水膜を有する基体、及びこの下地層及び撥水膜を有する基体を含む輸送機器用物品
JP7321655B2 (ja) 被膜の耐候性を評価する方法、該被膜の製膜方法及び該被膜を有する物品
WO2018034202A1 (fr) Composition
JPH0940910A (ja) 撥水処理剤
JP7397367B1 (ja) 組成物および物品
US20230257528A1 (en) Surface treating composition
JP2013129695A (ja) 撥水膜形成用組成物、撥水膜付き基体および輸送機器用物品
KR20220010452A (ko) 플루오로폴리에테르 변성 아미드실란 화합물, 표면처리제 조성물, 및 물품

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20791722

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20791722

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP