WO2022270318A1 - Composé éther contenant du fluor, mélange d'éther contenant du fluor, agent de revêtement, article et procédé de fabrication d'article - Google Patents

Composé éther contenant du fluor, mélange d'éther contenant du fluor, agent de revêtement, article et procédé de fabrication d'article Download PDF

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WO2022270318A1
WO2022270318A1 PCT/JP2022/023183 JP2022023183W WO2022270318A1 WO 2022270318 A1 WO2022270318 A1 WO 2022270318A1 JP 2022023183 W JP2022023183 W JP 2022023183W WO 2022270318 A1 WO2022270318 A1 WO 2022270318A1
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group
fluorine
formula
containing ether
ether compound
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PCT/JP2022/023183
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English (en)
Japanese (ja)
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隆太 高下
剛 長谷川
祥一 齊藤
英樹 富澤
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Ａｇｃ株式会社
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Priority to JP2023529823A priority Critical patent/JPWO2022270318A1/ja
Priority to KR1020237042244A priority patent/KR20240024804A/ko
Priority to CN202280043528.XA priority patent/CN117545792A/zh
Publication of WO2022270318A1 publication Critical patent/WO2022270318A1/fr

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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08G2150/00—Compositions for coatings
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers

Definitions

  • the present disclosure relates to fluorine-containing ether compounds, fluorine-containing ether mixtures, coating agents, articles, and methods for producing articles.
  • Fluorine-containing compounds exhibit high lubricity, water and oil repellency, and are therefore suitable for use as surface treatment agents. By imparting water and oil repellency to the surface of the base material with the surface treatment agent, dirt on the surface of the base material can be easily wiped off and the removability of the dirt can be improved.
  • a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain in which an ether bond is present in the fluoroalkylene chain is a compound with excellent flexibility, and is particularly excellent in removing stains such as oils and fats.
  • fluorine-containing ether compound compounds having a poly(oxyperfluoroalkylene) chain and having a hydrolyzable silyl group at the end thereof are widely used.
  • a mixture of a poly(oxyperfluoroalkylene) group-containing silane compound and a fluorine-containing compound has water repellency, oil repellency, antifouling properties, and waterproof properties, and also exhibits excellent friction durability.
  • Patent Document 2 discloses a fluorine-containing ether for vapor deposition, which contains a compound having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group, and a partial condensate of the compound, and is capable of forming a vapor deposition film having excellent friction durability. A composition is described.
  • the present disclosure relates to a fluorine-containing ether compound, a fluorine-containing ether mixture, a coating agent capable of forming a surface layer with excellent abrasion resistance, an article using these, and a method for producing the same.
  • X 1 each independently represents a monovalent organic group having a poly(oxyfluoroalkylene) chain
  • X 2 represents a divalent organic group, provided that both terminal atoms of X 2 bonded to two oxygen atoms in formula (A) are carbon atoms
  • L each independently represents a hydrolyzable group or a hydroxyl group
  • n each independently represents an integer of 0 to 2
  • X 2 includes an alkylene group, a fluoroalkylene group, or an etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of an al
  • X 2 contains a poly(oxyperfluoroalkylene) group.
  • X 2 includes a structure represented by ⁇ (OCF 2 ) m21 (OCF 2 CF 2 ) m22 ⁇ , wherein m21 is an integer of 1 or more and m22 is 1 or more
  • m21+m22 is an integer of 2 to 500.
  • X 2 is a poly(oxyperfluoroalkylene) group;
  • An alkylene group an etheric oxygen having an etheric oxygen atom between the carbon atoms of the alkylene group, which connects between the poly(oxyperfluoroalkylene) group and at least one of the two oxygen atoms in the formula (A) a divalent organic group selected from the group consisting of atom-containing groups, perfluoroalkylene groups, and combinations thereof;
  • X 1 represents a monovalent organic group having a poly(oxyfluoroalkylene) chain
  • each R 1 independently represents a monovalent hydrocarbon group
  • L each independently represents a hydrolyzable group or a hydroxyl group
  • n represents an integer of 0 to 2
  • X2 represents a divalent organic group, provided that both terminal atoms of X2 bonded to two hydroxyl groups in formula (Cd) are carbon atoms.
  • the molar ratio (M Cs /M Cd ) of the amount M Cs of the compound represented by the formula (Cs) to the amount M Cd of the compound represented by the formula (Cd) is 1 .5 to 4.0, the fluorine-containing ether compound according to ⁇ 7>.
  • the catalyst contains at least one selected from the group consisting of carboxylic acids, Lewis acids, substituted or unsubstituted pyridines, substituted or unsubstituted imidazoles, tertiary phosphines, amine compounds, and solid catalysts.
  • X 1 represents a monovalent organic group having a poly(oxyfluoroalkylene) chain
  • each R 1 independently represents a monovalent hydrocarbon group
  • L each independently represents a hydrolyzable group or a hydroxyl group
  • n represents an integer of 0 to 2
  • X2 represents a divalent organic group, provided that both terminal atoms of X2 bonded to two hydroxyl groups in formula (Cd) are carbon atoms.
  • the molar ratio (M Cs /M Cd ) of the amount M Cs of the compound represented by the formula (Cs) to the amount M Cd of the compound represented by the formula (Cd) is 1 .5 to 4.0, the method for producing a fluorine-containing ether compound according to ⁇ 10>.
  • the catalyst contains at least one selected from the group consisting of carboxylic acids, Lewis acids, substituted or unsubstituted pyridines, substituted or unsubstituted imidazoles, tertiary phosphines, amine compounds, and solid catalysts.
  • ⁇ 13> Contains two or more fluorine-containing ether compounds according to any one of ⁇ 1> to ⁇ 9>, or containing the fluorine-containing ether compound according to any one of ⁇ 1> to ⁇ 9> A fluorine-containing ether mixture containing one or more fluorine-containing ether compounds other than the fluorine-containing ether compound according to any one of ⁇ 1> to ⁇ 9>.
  • a coating agent comprising the fluorine-containing ether compound according to any one of ⁇ 1> to ⁇ 9> or the fluorine-containing ether mixture according to ⁇ 13>.
  • ⁇ 16> An article comprising a base material and a surface layer formed on the base material by the coating agent according to ⁇ 14> or ⁇ 15>.
  • a method for producing an article comprising applying the coating agent according to ⁇ 14> to a surface of a substrate by a dry coating method to form a surface layer on the substrate.
  • a method of manufacturing an article comprising:
  • a fluorine-containing ether compound a fluorine-containing ether mixture, a coating agent capable of forming a surface layer with excellent abrasion resistance, an article using these, and a method for producing the same are provided.
  • the term "process” includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. .
  • the numerical range indicated using “-” includes the numerical values before and after "-" as the minimum and maximum values, respectively.
  • each component may contain multiple types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
  • the terms "alkyl group” and “alkylene group” mean unsubstituted alkyl groups and unsubstituted alkylene groups, respectively, unless otherwise specified that they have substituents.
  • the fluorine ether compound of the present disclosure is represented by the following formula (A).
  • X 1 each independently represents a monovalent organic group having a poly(oxyfluoroalkylene) chain
  • X 2 represents a divalent organic group, provided that both terminal atoms of X 2 bonded to two oxygen atoms in formula (A) are carbon atoms
  • each R 1 independently represents a monovalent hydrocarbon group
  • L each independently represents a hydrolyzable group or a hydroxyl group
  • n each independently represents an integer of 0 to 2;
  • the fluorine-containing ether compound is also referred to as a "specific fluorine-containing ether compound".
  • each group of the specific fluorine-containing ether compound may be indicated as follows.
  • the specific fluorine ether compound has a structure represented by (S) group-(D) group-(S) group.
  • the two (S) groups may be the same or different. From the viewpoint of manufacturability, the two (S) groups are preferably the same.
  • Patent Document 1 describes a composition obtained by mixing a poly(oxyperfluoroalkylene) group-containing silane compound and a monovalent poly(oxyperfluoroalkylene) group-containing alcohol compound.
  • the specific fluorine-containing ether compound has a structure in which a plurality of (S) groups having poly(oxyfluoroalkylene) chains are linked via (D) groups, the surface layer is formed using the specific fluorine-containing ether compound. It is believed that a stronger coating is formed when formed.
  • a partial condensate of a compound having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group described in Patent Document 2 has a plurality of poly(oxyperfluoroalkylene) chains linked via Si—O—Si bonds. It is In contrast, the specific fluorine-containing ether compound has a plurality of poly(oxyfluoroalkylene) chains linked via Si—O—C bonds. Since a plurality of (S) groups are linked via the (D) group, it is believed that a stronger coating is formed when the surface layer is formed using the specific fluorine-containing ether compound.
  • the specific fluorine ether compound is, for example, reacted with a compound having a poly(oxyfluoroalkylene) chain and a hydrolyzable silyl group and a diol at a molar ratio of about 2:1 in the presence of a catalyst to transesterify.
  • a catalyst to transesterify obtained by Said reaction forms a Si--O--C bond between the hydrolyzable silyl group and the two hydroxyl groups of the diol.
  • the fluorine-containing ether compounds of the present disclosure have two (S) groups.
  • the (S) group preferably has a structure derived from a compound represented by formula (Cs) described below.
  • X1 is a monovalent organic group having a poly(oxyfluoroalkylene) chain.
  • a poly(oxyfluoroalkylene) chain includes a plurality of units represented by the following formula.
  • Formula: (OX) In the formula, each X independently represents a fluoroalkylene group.
  • the number of carbon atoms in the fluoroalkylene group in the poly(oxyfluoroalkylene) chain is preferably 1 to 20, more preferably 1 to 10, and 1 to 6 independently from the viewpoint of improving the abrasion resistance of the surface layer. is more preferred.
  • a fluoroalkylene group may be linear, branched or cyclic.
  • the number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times the number of carbon atoms, more preferably 1.7 to 2 times, from the viewpoint of improving the abrasion resistance of the surface layer.
  • the fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (perfluoroalkylene group). From the viewpoint of improving the abrasion resistance of the surface layer, the perfluoroalkylene group is preferable.
  • (OX) includes -OCHF-, -OCF 2 CHF-, -OCHFCF 2 - , -OCF 2 CH 2 -, -OCH 2 CF 2 -, -OCF 2 CF 2 CHF-, -OCHFCF 2 CF 2 - , -OCF2CF2CH2- , -OCH2CF2CF2- , -OCF2CF2CF2CH2- , -OCH2CF2CF2CF2- , -OCF2CF2CF2CF2CH _ _ _ _ _ _ _ _ _ 2- , -OCH2CF2CF2CF2- , -OCF2CF2CF2CF2CF2CH2- , -OCH2CF2CF2CF2CF2CF2- , -OCF2- _ _ _ _ _ _ _ _ _ _ _ _ 2- , -OCH2CF2CF2CF2- , -OCF2
  • the repeating number m of (OX) is an integer of 2 or more, preferably an integer of 2 to 500, more preferably an integer of 2 to 200, and even more preferably an integer of 5 to 150.
  • (OX) m may be a repetition of one type of (OX), or may contain two or more types of (OX).
  • the binding order of two or more (OX) is not limited, and may be arranged randomly, alternately, or in blocks.
  • Containing two or more types of (OX) means that, in the specific fluorine-containing ether compound, for example, two or more types of (OX) having different numbers of carbon atoms are present, two or more types of (OX) having different numbers of hydrogen atoms exists, two or more types of (OX) with different positions of hydrogen atoms exist, or the presence or absence of side chains even if the number of carbon atoms is the same, the type of side chain (the number of side chains, the number of side chains It means that there are two or more types of (OX) having different numbers of carbon atoms, etc.).
  • the poly(oxyfluoroalkylene) chain is preferably a poly(oxyfluoroalkylene) chain mainly composed of (OX), which is an oxyperfluoroalkylene group, from the viewpoint of forming a film having excellent fingerprint stain removability.
  • OX In the poly(oxyfluoroalkylene) chain represented by m , the ratio of the number of (OX) which is an oxyperfluoroalkylene group to the total number m of (OX) is preferably 50 to 100%, and 80 to 100 % is more preferred, and 90 to 100% is even more preferred.
  • the poly(oxyfluoroalkylene) chain includes a poly(oxyperfluoroalkylene) chain and a poly(oxyperfluoroalkylene) chain having one or two oxyfluoroalkylene units having hydrogen atoms at one end or both ends. more preferred.
  • two or more (OX) arrangements are represented as follows.
  • the structure represented by ⁇ (OCF 2 ) m21 (OCF 2 CF 2 ) m22 ⁇ indicates that m21 (OCF 2 ) and m22 (OCF 2 CF 2 ) are randomly arranged.
  • the structure represented by ( OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2 ) m25 is composed of m25 ( OCF2CF2 ) and m25 ( OCF2CF2CF2CF2 ) Indicates that they are arranged alternately.
  • (OX) m is represented by (OCH ma F (2-ma) ) m11 ⁇ (OC 2 H mb F (4-mb) ) m12 ⁇ (OC 3 H mc F (6-mc) ) m13 ⁇ (OC 4 H md F (8-md) ) m14 .(OC 5 H me F (10-me) ) m15 .(OC 6 H mf F (12-mf) ) m16 .(O-cycloC 4 H mg F (6- mg) ) m17 is preferred.
  • -cycloC 4 H mg F (6-mg) represents a fluorocyclobutane-diyl group, preferably a fluorocyclobutane-1,2-diyl group.
  • ma is 0 or 1
  • mb is an integer of 0 to 3
  • mc is an integer of 0 to 5
  • md is an integer of 0 to 7
  • me is an integer of 0 to 9.
  • mf is an integer from 0 to 11
  • mg is an integer from 0 to 5.
  • m11, m12, m13, m14, m15, m16 and m17 are each independently an integer of 0 or more, preferably 150 or less.
  • m11+m12+m13+m14+m15+m16+m17 is an integer of 2 or more, preferably an integer of 2 to 500, more preferably an integer of 2 to 200, and even more preferably an integer of 5 to 150.
  • m12 is preferably an integer of 2 or more, more preferably an integer of 2 to 200.
  • C 3 H mc F (6-mc) , C 4 H md F (8-md) , C 5 H me F (10-me) and C 6 H mf F (12-mf) are also linear or a branched chain, and a straight chain is preferred from the standpoint of more excellent abrasion resistance of the surface layer.
  • the above formula represents the type and number of units, and does not represent the arrangement of the units. That is, m11 to m16 represent the number of units.
  • m11 represents a block in which m11 (OCH ma F (2-ma) ) units are consecutive. is not.
  • the order of (OCH ma F (2-ma) ) to (O-cycloC 4 H mg F (6-mg) ) does not indicate that they are arranged in that order.
  • the arrangement of different units is a random arrangement or an alternate arrangement.
  • each oxyfluoroalkylene unit may be the same or different.
  • m11 is 2 or more
  • multiple (OCH ma F (2-ma) ) may be the same or different.
  • (OX) m preferably has the following structure. ⁇ ( OCF2 ) m21 ( OCF2 CF2) m22 ⁇ , ( OCF2CF2 ) m23 , ( OCF2CF2CF2 ) m24 , ( OCF2CF2 - OCF2CF2CF2 ) m25 , ( OCF2CF2CF2CF2 ) m26 ( OCF2 ) m27 , ( OCF2CF2CF2CF2CF2 ) m26 ( OCF2CF2 ) m27 , ( OCF2CF2CF2CF2CF2CF2 ) m26 ( OCF2 ) m27 , ( OCF2CF2CF2CF2CF2CF2 ) m26 ( OCF2 ) m27 , ( OCF2CF2CF2CF2CF2CF2 ) m26 ( OCF2 ) m27 , ( OCF2CF2CF2CF2CF2 ) m26 ( OCF
  • m21 is an integer of 1 or more
  • m22 is an integer of 1 or more
  • m21+m22 is an integer of 2 to 500
  • m23 and m24 are each independently an integer of 2 to 500
  • m25 is It is an integer of 1-250
  • m26 and m27 are each independently an integer of 1 or more
  • m26+m27 is an integer of 2-500
  • m28 is an integer of 1-250.
  • (OX) m is preferably the following structure from the viewpoint of easy production of the specific fluorine-containing ether compound. ⁇ ( OCF2 ) m21 ( OCF2 CF2) m22 ⁇ , ( OCF2CF2 ) m24 , (OCF 2 CF 2 ) 2 ⁇ (OCF 2 ) m21 (OCF 2 CF 2 ) m22-2 ⁇ , ( OCF2CF2 - OCF2CF2CF2 ) m25-1 OCF2CF2 , _ ( OCF2CF2CF2CF2CF2 - OCF2 ) m28 , ( OCF2CF2CF2CF2CF2CF2 - OCF2 ) m28 , _ ( OCF2CF2 - OCF2CF2CF2 ) m28-1 OCF2CF2 , _ _ ( OCF2CF2 - OCF2CF2CF2CF2CF2 ) m28-1 OCF2CF2 , _
  • the ratio of m22 to m21 (m22/m21) is from 0.05 to 10.00 is preferred, 0.08 to 2.00 is more preferred, 0.10 to 1.00 is particularly preferred, and 0.12 to 0.85 is most preferred.
  • m21>m22 in ⁇ (OCF 2 ) m21 (OCF 2 CF 2 ) m22 ⁇ , it is preferable that m21>m22.
  • m21 is preferably 2 to 200 and m22 is 2 to 100, m21 is 10 to 150 and m22 is 5 to 50. is more preferable.
  • m25 is preferably 2 to 100, more preferably 5 to 20, even more preferably 7 to 15.
  • X 1 may have a group represented by R f1 -(OX) m -* and a linking group linked to *.
  • R f1 represents a fluoroalkyl group
  • each X independently represents a fluoroalkylene group
  • m represents an integer of 2 or more.
  • R f1 is preferably a perfluoroalkyl group.
  • the number of carbon atoms in the perfluoroalkyl group is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 6, from the viewpoint of improving the abrasion resistance of the surface layer.
  • Perfluoroalkyl groups may be linear, branched or cyclic.
  • perfluoroalkyl groups include CF 3 —, CF 3 CF 2 —, CF 3 CF 2 CF 2 —, CF 3 CF 2 CF 2 —, CF 3 CF 2 CF 2 CF 2 —, CF 3 CF 2 CF 2 CF 2 —, CF 3 CF 2 CF 2 CF 2 — and CF 3 CF(CF 3 )—, and from the viewpoint of more excellent water and oil repellency of the surface layer, CF 3 —, CF 3 CF 2 —, CF 3 CF 2 —, and CF 3 CF 2 CF 2 — are preferred.
  • X 1 may have a group represented by Z—(OX) m —* and a linking group linked to *.
  • Z represents a monovalent organic group other than a fluoroalkyl group
  • X each independently represents a fluoroalkylene group
  • m represents an integer of 2 or more.
  • the linking groups connected to * of the group represented by R f1 -(OX) m -* and the group represented by Z-(OX) m -* are, respectively, these groups and -Si(R 1 ) n L 2-n is a divalent group that connects with the Si atom in the group represented by -O-.
  • divalent group examples include an alkylene group, a fluoroalkylene group, an etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group, -Si(R 6 ) 2 -, - Si(CH 3 ) 2 —Ph—Si(CH 3 ) 2 —, divalent organopolysiloxane residues and combinations thereof.
  • the atom described on the left side is bound to *.
  • the divalent group may further include -C(O)NR 6 -, -C(O)O-, -C(O)-, -NR 6 -, -S-, -NHC(O)O-, - NHC(O)NR 6 —, —SO 2 NR 6 — and the like may be included.
  • each R 6 is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group.
  • the number of carbon atoms in the alkyl group of R 6 is preferably 1 to 3 from the viewpoint of ease of production.
  • the hydrogen atoms in the alkyl groups to 6 is a group having a reactive silyl group represented by the formula -Si(R 1 ) n L 3-n , for example, -Si(R 1 ) n L 3 -n or an alkylene group -Si(R 1 ) n L 3-n . Details of the reactive silyl group are as described below.
  • the number of carbon atoms in the alkylene group —Si(R 1 ) n L 3-n is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6.
  • the alkylene group that is the linking group that is linked to * is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and still more preferably an alkylene group having 1 to 11 carbon atoms.
  • the fluoroalkylene group which is a linking group linked to *, has at least one fluorine atom and is preferably a fluoroalkylene group having 1 to 20 carbon atoms, more preferably a fluoroalkylene group having 1 to 10 carbon atoms. 1 to 6 fluoroalkylene groups are more preferred. Among them, a perfluoroalkylene group having the number of carbon atoms described above is preferable.
  • the total carbon number of the etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group, which is the linking group linked to *, is preferably 2 to 10, more preferably 2 to 6. , 2 to 4 are more preferred.
  • the etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group includes poly(oxyalkylene) groups and the like. Examples of the poly(oxyalkylene) group include groups having an alkylene group having 1 to 10 carbon atoms in each oxyalkylene unit, and the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3.
  • the plurality of oxyalkylene units in the poly(oxyalkylene group) may be one or two or more, and preferably one or two from the viewpoint of ease of production.
  • An alkylene group, a fluoroalkylene group, and an etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group may each independently be linear or branched. .
  • the linking group that is linked to * includes a combination of —C(O)NR 6 — and a linear or branched alkylene group optionally substituted with a reactive silyl group. be done.
  • the linking group linked to * may have one or more reactive silyl groups represented by the formula —Si(R 1 ) n L 3-n .
  • the details of the reactive silyl group represented by the formula —Si(R 1 ) n L 3-n are as described later.
  • the total number of reactive silyl groups in the linking group linked to * is preferably 0-2.
  • Z in the group represented by the formula Z-(OX) m -* is a monovalent organic group other than a fluoroalkyl group.
  • the monovalent organic group represented by Z is, for example, a reactive silyl group represented by the formula —Si(R 1 ) n L 3-n added to the above-described group described as the linking group linked to *. It may be connected.
  • any of the groups described as the linking groups linked to * above, the other bond on the side opposite to the bonding site with * is It may be bonded to a reactive silyl group represented by the formula —Si(R 1 ) n L 3-n .
  • the monovalent organic group represented by Z may be a group represented by Z 1 -X-, where Z 1 represents a monovalent organic group other than a fluoroalkyl group, X has the same definition as X in (OX) m , and X may be the same as or different from X in (OX) m .
  • Z 1 is a group of the formula —Si(R 1 ) n It may be bonded to a reactive silyl group represented by L 3-n .
  • X 1 is Si(R 1 ) n L 3-n -(group*)-X-(OX) m -(group*)- has a structure represented by
  • (group *) represents any of the groups described as the linking groups linked to * above, and two (groups *) may be the same or different. From the viewpoint of ease of production, the two (groups*) are preferably the same, and the same (groups*) are more preferably arranged symmetrically about -X-(OX) m -. preferable.
  • the details of the reactive silyl group represented by the formula —Si(R 1 ) n L 3-n are as described later.
  • the number of reactive silyl groups that Z has is preferably 1 to 5, more preferably 1 to 3.
  • linking group linked to * are as follows. ** in the following specific example represents the linking position to Si in formula (A).
  • X 2 represents a divalent organic group, provided that both of X 2 bonded to two oxygen atoms in formula (A) The terminal atoms are carbon atoms.
  • X 2 is preferably an alkylene group, a fluoroalkylene group, an etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of an alkylene group or a fluoroalkylene group, or a combination thereof.
  • the number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, from the viewpoint of excellent abrasion resistance.
  • the number of carbon atoms in the fluoroalkylene group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, from the viewpoint of excellent abrasion resistance.
  • the fluoroalkylene group is preferably a perfluoroalkylene group or a group in which an alkylene group having 1 to 3 carbon atoms is bonded to both ends or one end of a perfluoroalkylene group.
  • the etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of an alkylene group or a fluoroalkylene group contained in X 2 includes a poly(oxyalkylene) group and a poly(oxyfluoroalkylene) group. mentioned.
  • the poly(oxyalkylene) group include groups having an alkylene group having 1 to 20 carbon atoms in each oxyalkylene unit, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
  • the plurality of oxyalkylene units in the poly(oxyalkylene group) may be one or two or more, and preferably one or two from the viewpoint of ease of production.
  • Examples of the poly(oxyfluoroalkylene) group include groups in which the alkylene group of the poly(oxyalkylene) group is substituted with one or more fluorine atoms, and a poly(oxyperfluoroalkylene) group is preferred. Among them, a poly(oxyfluoroalkylene) group represented by (OX) m is preferable. Here, the details of (OX) m can be applied to the details of (OX) m in X 1 of the (S) group.
  • X 2 preferably includes a structure represented by ⁇ (OCF 2 ) m21 (OCF 2 CF 2 ) m22 ⁇ .
  • m21 is an integer of 1 or more
  • m22 is an integer of 1 or more
  • m21+m22 is an integer of 2-500. Details of ⁇ (OCF 2 ) m21 (OCF 2 CF 2 ) m22 ⁇ are described above for the structure of ⁇ (OCF 2 ) m21 (OCF 2 CF 2 ) m22 ⁇ , which is an aspect of (OX) m in the (S) group. applicable. In ⁇ (OCF 2 ) m21 (OCF 2 CF 2 ) m22 ⁇ , it is preferable that m21>m22.
  • -X 2 - is a poly(oxyperfluoroalkylene) group, an alkylene group connecting between the poly(oxyperfluoroalkylene) group and at least one of the two oxygen atoms in the formula (A), an alkylene group A divalent organic group selected from the group consisting of a carbon atom-an ethereal oxygen atom-containing group having an etheric oxygen atom between the carbon atoms, a perfluoroalkylene group, and combinations thereof preferable.
  • the divalent organic group is an alkylene group
  • the number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, from the viewpoint of excellent abrasion resistance.
  • Alkylene groups may be linear or branched.
  • the divalent organic group is an etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group
  • the total carbon number of the etheric oxygen atom-containing group is From the standpoint of superiority, 2 to 10 are preferred, 2 to 6 are more preferred, and 2 to 4 are even more preferred.
  • the etheric oxygen atom-containing group may be linear or branched.
  • the etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group includes poly(oxyalkylene) groups and the like.
  • Examples of the poly(oxyalkylene) group include groups having an alkylene group having 1 to 10 carbon atoms in each oxyalkylene unit, and the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3.
  • the plurality of oxyalkylene units in the poly(oxyalkylene group) may be one or two or more, and preferably one or two from the viewpoint of ease of production.
  • Examples of the perfluoroalkylene group include the perfluoroalkylene groups exemplified as X in (OX) m described above.
  • the fluorine-containing ether compound is obtained by subjecting a compound represented by the following formula (Cs) and a compound represented by the following formula (Cd) to transesterification in the presence of a catalyst.
  • X 1 represents a monovalent organic group having a poly(oxyfluoroalkylene) chain
  • each R 1 independently represents a monovalent hydrocarbon group
  • L each independently represents a hydrolyzable group or a hydroxyl group
  • n represents an integer of 0 to 2
  • X2 represents a divalent organic group, provided that both terminal atoms of X2 bonded to two hydroxyl groups in formula (Cd) are carbon atoms.
  • a specific fluorine-containing ether compound can be produced by the production method described above.
  • the compound represented by formula (Cs) may be referred to as “compound (Cs)”
  • the compound represented by formula (Cd) may be referred to as “compound (Cd)”.
  • —Si(R 1 ) n L 3-n in formula (Cs) is a reactive silyl group.
  • a reactive silyl group means a hydrolyzable silyl group and a silanol group (Si—OH).
  • a hydrolyzable silyl group becomes a silanol group represented by Si—OH through a hydrolysis reaction.
  • the silanol group can further form a Si--O--C bond by transesterification with the hydroxyl group of the compound represented by (Cd).
  • Each R 1 is independently a monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group.
  • the number of carbon atoms in R 1 is preferably 1-6, more preferably 1-3, even more preferably 1-2.
  • Each L is independently a hydrolyzable group or a hydroxyl group.
  • the hydrolyzable group represented by L is a group that becomes a hydroxyl group through a hydrolysis reaction.
  • Examples of the hydrolyzable group L include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (--NCO).
  • the alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable.
  • the aryloxy group an aryloxy group having 3 to 10 carbon atoms is preferred.
  • the aryl group of the aryloxy group may be an aryl group containing no heteroatom or a heteroaryl group.
  • a chlorine atom is preferable as the halogen atom.
  • As the acyl group an acyl group having 1 to 6 carbon atoms is preferred.
  • an acyloxy group having 1 to 6 carbon atoms is preferred.
  • L is preferably an alkoxy group having 1 to 4 carbon atoms and a halogen atom.
  • L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing during application and excellent storage stability of the fluorine-containing ether compound, and when long-term storage stability of the fluorine-containing ether compound is required.
  • n is an integer of 0-2. n is preferably 0 or 1, more preferably 0.
  • the adhesion of the surface layer to the base material becomes stronger.
  • n is 1 or less, multiple Ls present in one molecule may be the same or different. From the viewpoint of availability of raw materials and ease of production of the fluorine-containing ether compound, it is preferable that the plurality of L's are the same.
  • n is 2, multiple R 2 present in one molecule may be the same or different. From the viewpoint of the availability of raw materials and the ease of production of the fluorine-containing ether compound, they are preferably the same.
  • the molar ratio (M Cs /M Cd ) of the amount M Cs of the compound (Cs) to the amount M Cd of the compound (Cd) is 1. 1 to 10 are preferred, 1.3 to 7.0 are more preferred, and 1.5 to 4.0 are even more preferred.
  • the transesterification reaction between the compound (Cs) and the compound (Cd) is performed, for example, by adding a catalyst to a mixture of the compound (Cs) and the compound (Cd) or a mixture of these dissolved in a solvent to react both compounds. It is done by
  • Catalysts include acid catalysts and nucleophilic catalysts.
  • Acid catalysts include Lewis acids such as titanium alkoxide; and acids such as sulfonic acid, phosphonic acid, hydrochloric acid, sulfuric acid, and carboxylic acids. is more preferred.
  • Nucleophilic catalysts include substituted or unsubstituted pyridine; substituted or unsubstituted imidazole; tertiary phosphines such as triphenylphosphine; amine compounds such as 1,4-diazabicyclo[2.2.2]octane; Of these, substituted or unsubstituted pyridine is preferred from the viewpoint of efficient transesterification.
  • the catalyst also includes solid catalysts such as zeolite and amberlyst.
  • the catalyst consists of a carboxylic acid, a Lewis acid, a substituted or unsubstituted pyridine, a substituted or unsubstituted imidazole, a tertiary phosphine, an amine compound, and a solid catalyst. At least one selected from the group is preferred.
  • the solvent is not particularly limited, and may be adjusted as appropriate according to the type of compound (Cs), compound (Cd) and catalyst.
  • the solvent can be appropriately selected from, for example, fluorine-based organic solvents and non-fluorine-based organic solvents that can be used in coating agents described later, or mixed solvents thereof.
  • the reaction temperature and reaction time may be appropriately adjusted according to the type of compound (Cs), compound (Cd), catalyst, etc.
  • the reaction may be carried out at 80-120°C for 10-100 hours.
  • the fluorine-containing ether mixture of the present disclosure contains two or more specific fluorine-containing ether compounds, or one or more specific fluorine-containing ether compounds and a fluorine-containing ether compound other than the specific fluorine-containing ether compounds.
  • the fluorine-containing ether mixture is also referred to as "specific fluorine-containing ether mixture”.
  • a specific fluorine-containing ether mixture is a mixture of two or more fluorine-containing ether compounds containing a specific fluorine-containing ether compound.
  • the fluorine-containing ether compounds other than the specific fluorine-containing ether compound may be used singly or in combination of two or more.
  • fluorine-containing ether compounds other than the specific fluorine-containing ether compounds include those described in the following documents. perfluoropolyether-modified aminosilanes described in JP-A-11-029585 and JP-A-2000-327772; a silicon-containing organic fluorine-containing polymer described in Japanese Patent No. 2874715; Organosilicon compounds described in JP-A-2000-144097, Fluorinated siloxane described in JP-T-2002-506887, Organosilicone compounds described in JP-T-2008-534696, a fluorinated modified hydrogen-containing polymer described in Japanese Patent No. 4138936; The compounds described in US Patent Application Publication No.
  • fluorine-containing ether compounds other than specific fluorine-containing ether compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) manufactured by AGC. ) S550, Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509 manufactured by Daikin Industries, Ltd., Fomblin (registered trademark) of Solvay, Fluorolink (registered trademark) and Krytox (registered trademark) manufactured by Chemours.
  • Fluorine-containing ether compounds other than the specific fluorine-containing ether compound also include fluorine-containing ether compounds that are by-produced in the production process of the specific fluorine-containing ether compound.
  • Examples of the by-product fluorine-containing ether compound include CF 3 CF 2 CF 2 O[CF 2 obtained as a by-product of the fluorine-containing ether compound produced by the method described in Example 13-7 of WO 2018/216630.
  • the content of the fluorine-containing ether compound other than the specific fluorine-containing ether compound is preferably 0% by mass or more and less than 90% by mass, more preferably 0% by mass or more and less than 70% by mass, based on the total mass of the specific fluorine-containing ether compound. , more preferably 0% by mass or more and less than 50% by mass, and particularly preferably 0% by mass or more and less than 30% by mass.
  • the coating agent of the present disclosure contains a specific fluorine-containing ether compound or a specific fluorine-containing ether mixture.
  • a specific fluorine-containing ether compound or a specific fluorine-containing ether mixture can be used alone to form a surface layer on a substrate (dry coating method described later).
  • a composition containing other components than the specific fluorine-containing ether compound or the specific fluorine-containing ether mixture may be used (dry coating method and wet coating method described later). .
  • a specific fluorine-containing ether compound, a specific fluorine-containing ether mixture, and a composition containing a specific fluorine-containing ether compound or a specific fluorine-containing ether mixture and other components, which are used for coating a substrate are all ""coatingagent".
  • the coating agent may contain a liquid medium.
  • liquid media include water and organic solvents.
  • a liquid medium refers to a medium that is liquid at 25°C.
  • the liquid medium preferably contains an organic solvent, and more preferably contains an organic solvent having a boiling point of 35 to 250° C. from the viewpoint of excellent coatability.
  • boiling point means normal boiling point.
  • the organic solvent include fluorine-based organic solvents and non-fluorine-based organic solvents, and from the viewpoint of excellent solubility, fluorine-based organic solvents are preferred.
  • An organic solvent may be used individually by 1 type, and may use 2 or more types together.
  • Fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and the like.
  • the fluorinated alkane is preferably a compound having 4 to 8 carbon atoms.
  • Examples of compounds having 4 to 8 carbon atoms include C 6 F 13 H (AC-2000: product name, manufactured by AGC), C 6 F 13 C 2 H 5 (AC-6000: product name, manufactured by AGC), C 2 F 5 CHFCHFCF 3 (Vertrell: product name, manufactured by Chemours) and the like.
  • Fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis(trifluoromethyl)benzene, and 1,4-bis(trifluoromethyl)benzene.
  • Fluoroalkyl ethers are preferably compounds having 4 to 12 carbon atoms. Examples of fluoroalkyl ethers include CF 3 CH 2 OCF 2 CF 2 H (AE-3000: product name, manufactured by AGC), C 4 F 9 OCH 3 (Novec-7100: product name, manufactured by 3M), and C 4 F.
  • Fluorinated alkylamines include perfluorotripropylamine, perfluorotributylamine, and the like.
  • Fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
  • non-fluorine organic solvent a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferable.
  • examples of such compounds include hydrocarbon-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, and alcohol-based organic solvents.
  • hydrocarbon-based organic solvents include hexane, heptane, cyclohexane, and the like.
  • Ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
  • ether-based organic solvents examples include diethyl ether, tetrahydrofuran, tetraethylene glycol dimethyl ether, and the like. Ethyl acetate, butyl acetate, etc. are mentioned as an ester type organic solvent.
  • alcoholic organic solvents include isopropyl alcohol, ethanol, n-butanol and the like.
  • the content of the liquid medium is preferably 70.00 to 99.99% by mass, more preferably 75.00 to 99.50% by mass, relative to the total mass of the coating agent.
  • the coating agent may contain components other than the specific fluorine-containing ether compound, the fluorine-containing ether compound other than the specific fluorine-containing ether compound, and the liquid medium.
  • the coating agent may contain by-products produced in the manufacturing process of the specific fluorine-containing ether compound and optionally other fluorine-containing ether compounds, residual unreacted raw materials, catalysts, and the like.
  • the coating agent may also contain additives such as acid catalysts and basic catalysts that promote hydrolysis and condensation reaction of the hydrolyzable silyl groups.
  • Acid catalysts include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like.
  • Basic catalysts include sodium hydroxide, potassium hydroxide, ammonia and the like.
  • the content of such components is the total mass of the components of the coating agent excluding the liquid medium. 0 to 10% by mass is preferable, 0 to 5% by mass is more preferable, and 0 to 1% by mass is even more preferable.
  • An article of the present disclosure has a substrate and a surface layer formed on the substrate with the coating agent.
  • the surface layer contains a compound obtained by hydrolysis reaction and condensation reaction of a specific fluorine-containing ether compound.
  • the thickness of the surface layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. When the thickness of the surface layer is equal to or greater than the lower limit, the effect of the surface layer can be obtained satisfactorily. When the thickness of the surface layer is equal to or less than the upper limit, the utilization efficiency of the coating agent is high.
  • the thickness of the surface layer is determined by obtaining an interference pattern of reflected X-rays by the X-ray reflectance method (XRR) using an X-ray diffractometer for thin film analysis (product name “ATX-G”, manufactured by RIGAKU). It can be calculated from the vibration period of the interference pattern.
  • Substrates include other items (stylus, etc.), substrates that may be used in contact with human fingers, substrates that may be held with human fingers during operation, and other items (placing table, etc.).
  • a substrate or the like on which it may be placed is preferred. Since the coating agent of the present disclosure can impart water and oil repellency and abrasion resistance to a substrate, it is particularly useful when using a substrate that requires imparting water and oil repellency and abrasion resistance.
  • Materials for the substrate include metal, resin, glass, sapphire, ceramic, stone, fiber, non-woven fabric, paper, wood, natural leather, artificial leather, and composite materials thereof.
  • the glass may be chemically strengthened.
  • the base material is preferably a touch panel base material or a display base material, and more preferably a touch panel base material.
  • the touch panel substrate preferably has translucency.
  • the term "having translucency" means that the vertical incidence type visible light transmittance according to JIS R3106:2019 (ISO 9050:2003) is 25% or more.
  • Glass or transparent resin is preferable as the material of the touch panel substrate. Interior goods; transportation equipment (automobiles, etc.); signboards or bulletin boards; drinking vessels or tableware; water tanks; packaging containers; glass or resin used for art, sports or games;
  • As the base material glass or resin used for exterior parts (excluding display parts) of devices such as mobile phones (smartphones, etc.), personal digital assistants, game machines, remote controllers, etc. is also preferable.
  • the shape of the substrate may be plate-like, film-like, or the like.
  • the article is a touch panel, and the surface layer is formed on the surface of a member that constitutes the surface of the touch panel that is touched by a finger.
  • the surface layer may be formed directly on the surface of the substrate, or may be formed on the substrate via another film formed on the surface of the substrate.
  • the other films include compounds described in paragraphs 0089 to 0095 of International Publication No. WO 2011/016458, base films formed on the surface of the base material by treating the base material with SiO 2 or the like. be done.
  • Articles of the present disclosure can be manufactured, for example, in the following manner.
  • a method of manufacturing an article comprising applying the coating agent of the present disclosure to the surface of a substrate by a dry coating method to form a surface layer on the substrate.
  • a method of manufacturing an article comprising applying the coating agent of the present disclosure to the surface of a substrate by a dry coating method to form a surface layer on the substrate.
  • Dry coating methods include vacuum deposition, CVD, and sputtering.
  • the vacuum deposition method is preferable from the viewpoint of suppressing the decomposition of the specific fluorine-containing ether compound and from the viewpoint of the simplicity of the apparatus.
  • a pellet-like material obtained by impregnating a metal porous material such as iron or steel with a coating agent containing a liquid medium and drying may be used.
  • wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure. A coat method and the like can be mentioned.
  • the drying temperature of the coating film is preferably 20 to 200°C, more preferably 80 to 160°C.
  • a specific fluorine-containing ether compound is hydrolyzed in advance using a catalyst such as an acid catalyst or a basic catalyst, and a composition containing the hydrolyzed compound and a liquid medium is used as a coating agent. good too.
  • composition 1 A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-1) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 1 was obtained by distilling off the solvent under reduced pressure.
  • hydrofluoroether manufactured by 3M, trade name: Novec HFE-7300
  • Example 2 A mixture containing 0.30 g of compound (A-2) and 0.15 g of compound (B-1) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 2 was obtained by distilling off the solvent under reduced pressure.
  • hydrofluoroether manufactured by 3M, trade name: Novec HFE-7300
  • Example 3 A mixture containing 0.40 g of compound (A-3) and 0.15 g of compound (B-1) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 3 was obtained by distilling off the solvent under reduced pressure.
  • hydrofluoroether manufactured by 3M, trade name: Novec HFE-7300
  • Example 4 A mixture containing 0.44 g of compound (A-4) and 0.15 g of compound (B-1) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 4 was obtained by distilling off the solvent under reduced pressure.
  • hydrofluoroether manufactured by 3M, trade name: Novec HFE-7300
  • Example 5 A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-2) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 5 was obtained by distilling off the solvent under reduced pressure.
  • hydrofluoroether manufactured by 3M, trade name: Novec HFE-7300
  • Example 6 A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-3) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 6 was obtained by distilling off the solvent under reduced pressure.
  • hydrofluoroether manufactured by 3M, trade name: Novec HFE-7300
  • Example 7 A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-1) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. 1.0 mg of acetic acid was added and reacted at 100° C. to obtain composition 7.
  • hydrofluoroether manufactured by 3M, trade name: Novec HFE-7300
  • Example 8 0.50 g of compound (A-1), 0.15 g of compound (B-1) and 1.0 mg of pyridine were added, reacted at 100° C., and concentrated under reduced pressure to obtain composition 8.
  • Composition 9 was obtained by mixing 0.50 g of compound (A-1) and 0.15 g of compound (B-1).
  • Example 10 0.50 g of compound (A-1) was dissolved in hydrofluoroether (Novec HFE-7300, manufactured by 3M) to a concentration of 20% by mass. After adding 1.0 mg of water and reacting at 100° C., composition 10 was obtained by distilling off the solvent under reduced pressure.
  • hydrofluoroether Novec HFE-7300, manufactured by 3M
  • a base material non-alkali glass (Eagle XG: trade name, manufactured by Corning, 50 mm ⁇ 50 mm, thickness 0.5 mm)
  • the pressure in the vacuum deposition apparatus is 5 ⁇ 10 -3 Pa or less.
  • was evacuated to a pressure of A deposition vessel containing the composition prepared above at a distance of 1000 mm so as to face one main surface of the substrate is heated to 300 ° C. by resistance heating, and the composition is vacuum-deposited to a thickness of 10 nm.
  • a surface layer was formed.
  • the temperature of the composition in each example was 300°C. After that, the obtained substrate with a surface layer was heated at a temperature of 200° C. for 30 minutes (post-treatment).
  • composition prepared above was mixed with C 4 F 9 OC 2 H 5 (Novec-7200: trade name, manufactured by 3M) as a liquid medium, and the content of the fluorine-containing ether compound in the coating agent was A coating liquid of 0.1% by mass was prepared.
  • Alkali-free glass (Eagle XG: trade name, manufactured by Corning Incorporated, 50 mm ⁇ 50 mm, thickness 0.5 mm) was prepared as the substrate.
  • the coating agent formed on the substrate is heated at 120 ° C. for 10 It was dried for a minute to obtain a base material with a surface layer.
  • the thickness of the surface layer was 10 nm.
  • ⁇ Evaluation method> [Initial water contact angle] The contact angle of approximately 2 ⁇ L of distilled water placed on the surface of the surface layer was measured using a contact angle measurement device (manufactured by Kyowa Interface Science Co., Ltd., DM-500). Measurements were performed at five different points on the surface of the surface layer, and the average value was calculated. The 2 ⁇ method was used to calculate the contact angle. Evaluation criteria are as follows. A: 115 degrees or more. B: 105 degrees or more and less than 115 degrees.
  • Example 9 in which the compounds (A-1) and (B-1) were mixed without using a catalyst, the abrasion resistance of the surface layer was inferior to those in Examples 1-8.
  • Example 10 in which a self-condensate of compound (A-1) was formed, the abrasion resistance of the surface layer was inferior to those in Examples 1-8. All evaluations of the initial contact angle were good.

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Abstract

La présente invention concerne : un composé éther contenant du fluor, représenté par la formule (A) X1-Si(R1)nL2-n-O-X2-O-Si(R1)nL2-n-X1 (dans la formule (A), chaque X1 représente indépendamment un groupe organique monovalent ayant une chaîne poly(oxyfluoroalkylène), X2 représente un groupe organique divalent, les atomes aux deux extrémités de X2 liés aux deux atomes d'oxygène dans la formule (A) sont tous les deux des atomes de carbone, chaque R1 représente indépendamment un groupe hydrocarboné monovalent, chaque L représente indépendamment un groupe hydrolysable ou un groupe hydroxyle, et chaque n représente indépendamment un nombre entier de 0 à 2 ; un procédé de production dudit composé ; un mélange d'éther contenant du fluor et un agent de revêtement qui contiennent ledit composé ; et un article utilisant ledit composé et un procédé de fabrication dudit article.
PCT/JP2022/023183 2021-06-21 2022-06-08 Composé éther contenant du fluor, mélange d'éther contenant du fluor, agent de revêtement, article et procédé de fabrication d'article WO2022270318A1 (fr)

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CN202280043528.XA CN117545792A (zh) 2021-06-21 2022-06-08 含氟醚化合物、含氟醚混合物、涂布剂、物品、及物品的制造方法

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JP2019035070A (ja) * 2017-08-18 2019-03-07 Ａｇｃ株式会社 含フッ素エーテル化合物の製造方法、物品の製造方法
JP2020196898A (ja) * 2015-09-01 2020-12-10 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、コーティング液および物品

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KR102559704B1 (ko) 2017-06-02 2023-07-25 에이지씨 가부시키가이샤 증착용 함불소 에테르 조성물, 그리고 증착막이 형성된 물품 및 그 제조 방법

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JPH06296850A (ja) * 1993-02-18 1994-10-25 Minnesota Mining & Mfg Co <3M> 分解性弗素化アルコキシシラン界面活性剤及びそれからの防水性塗布剤
JP2020196898A (ja) * 2015-09-01 2020-12-10 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、コーティング液および物品
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