WO2020111009A1 - Composé fluoré, composition comprenant un composé fluoré, liquide de revêtement, et article ainsi que procédé de fabrication de celui-ci - Google Patents

Composé fluoré, composition comprenant un composé fluoré, liquide de revêtement, et article ainsi que procédé de fabrication de celui-ci Download PDF

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Publication number
WO2020111009A1
WO2020111009A1 PCT/JP2019/046024 JP2019046024W WO2020111009A1 WO 2020111009 A1 WO2020111009 A1 WO 2020111009A1 JP 2019046024 W JP2019046024 W JP 2019046024W WO 2020111009 A1 WO2020111009 A1 WO 2020111009A1
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group
fluorine
compound
carbon atoms
atom
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PCT/JP2019/046024
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English (en)
Japanese (ja)
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啓吾 松浦
誠人 宇野
英一郎 安樂
豊和 遠田
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Ａｇｃ株式会社
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Publication of WO2020111009A1 publication Critical patent/WO2020111009A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • 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

Definitions

  • the present invention relates to a fluorine-containing compound, a composition containing a fluorine-containing compound, a coating liquid, an article and a method for producing the same.
  • a fluorine-containing compound having a fluorine-containing organic group such as a fluoroalkyl group or a fluoropolyether chain and a hydrolyzable silyl group can form a surface layer having high lubricity, water repellency and oil repellency on the surface of a substrate. Therefore, it is suitably used as a surface treatment agent.
  • the surface-treating agent containing a fluorine-containing compound has a property that the water and oil repellency does not easily deteriorate even if the surface layer is repeatedly rubbed with a finger (rubbing resistance), and a property that fingerprints attached to the surface layer can be easily removed by wiping ( It is used in applications where it is required to maintain fingerprint stain removability) for a long period of time, for example, as a member constituting a surface of a touch panel to be touched by a finger, an eyeglass lens, and a surface treatment agent for a display of a wearable terminal.
  • a fluorine-containing compound having a fluoropolyether chain and a hydrolyzable silyl group has been proposed as a fluorine-containing compound capable of forming a surface layer having excellent abrasion resistance and fingerprint stain removability on the surface of a substrate (Patent Document 1-4).
  • the present invention provides a fluorine-containing compound capable of forming a surface layer having excellent fingerprint stain removability and abrasion resistance, a composition containing a fluorine-containing compound and a coating liquid, an article having a surface layer excellent in fingerprint stain removability and abrasion resistance, and
  • the purpose is to provide a manufacturing method.
  • the present invention provides a fluorine-containing compound, a fluorine-containing compound-containing composition, a coating liquid, an article, and a method for producing an article, each of which has the constitutions [1] to [14] below.
  • the linking group has a site in which two or more polar groups are bonded in series via a divalent organic group having 1 to 20 carbon atoms,
  • the polar group is C(O)NH, NHC(O), NH, NHC(O)NH, NHC(S)NH, S(O) 2 NH, NHS(O) 2 , C(O), C( OH), C(OR 4 ), P(O), S(O), C[
  • a fluorine-containing compound which is a compound represented by the following formula (1A) or a compound represented by the following formula (1B).
  • [T ⁇ ] b2 [R f ⁇ ] a2 Q 2 ⁇ Q f ⁇ Q 2 [ ⁇ R f ] a2 [ ⁇ T] b2
  • R f is a fluoroalkyl group (provided that at least one fluorine atom is bonded to the terminal carbon atom on the Q 1 and Q 2 side) or a carbon-carbon atom of a fluoroalkyl group having 2 or more carbon atoms.
  • Q f represents a fluoroalkylene group (provided that at least one fluorine atom is bonded to the terminal carbon atom on the Q 2 side), or —O between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms.
  • Q 1 is an a1+b1 valent linking group having a site in which two or more polar groups are bonded in series via a divalent organic group having 1 to 20 carbon atoms
  • Q 2 is an a2+b2+1 valent linking group having a site in which two or more polar groups are bonded in series via a divalent organic group having 1 to 20 carbon atoms
  • the two Q 2 are the same.
  • the polar group is C(O)NH, NHC(O), NH, NHC(O)NH, NHC(S)NH, S(O) 2 NH, NHS(O) 2 , C(O), C( OH), C(OR 4 ), P(O), S(O), C[OP(O)(OR 4 ) 2 ], C[OS(O) 2 R 4 ] and C[OC(O)R.
  • R 4 is an alkyl group
  • R is an alkyl group
  • L is a hydrolyzable group or a hydroxyl group
  • two or more Ls may be the same or different
  • a1 is an integer of 1 or more
  • a2 is an integer of 0 or more
  • R f of 2 or more may be the same or different
  • b1 and b2 are each an integer of 1 or more
  • Ts of 2 or more may be the same or different
  • c is 2 or 3.
  • R f1 is a fluoroalkyl group having 1 to 6 carbon atoms (however, when m is 0, at least one fluorine atom is bonded to the terminal carbon atom on the Q 1 or Q 2 side), R f2 is a fluoroalkylene group having 1 to 6 carbon atoms (provided that at least one fluorine atom is attached to the Q 1 or Q 2 side terminal carbon atom of R f2 which bind to Q 1 or Q 2. ), and m is an integer of 0 or more, and when m is 2 or more, (OR f2 ) m may be composed of two or more kinds of OR f2 .
  • a group having -O- between the carbon-carbon atoms of the above alkylene group and having -O- at the terminal on the side not connected to Si, and two or more Q 22 s may be the same or different.
  • Q 23 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and two Q 23 may be the same or different
  • Q 24 is Q 22 when the atom in Z to which Q 24 is bonded is a carbon atom
  • two or more Q 24 are the same.
  • Q 25 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and 2 or more Q 25 may be the same or different
  • Q 26 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms
  • Q 27 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms
  • Z is a group having an a1+b1 valent or a2+b2+1 valent ring structure having a carbon atom or a nitrogen atom to which Q 14 directly bonds and a carbon atom or a nitrogen atom to which Q 24 directly bonds
  • R 1 is a hydrogen atom or an alkyl group, if Q 1 or Q 2 has the R 1 2 or more, 2 or more of R 1 may be the same or different and R
  • [6] The fluorinated compound according to any one of [2] to [5], wherein the fluorinated compound is a compound represented by the above formula (1A).
  • a fluorine-containing compound-containing composition comprising at least one fluorine-containing compound according to any one of the above [1] to [6] and another fluorine-containing compound.
  • a coating liquid comprising the fluorine-containing compound according to any one of [1] to [6] or the fluorine-containing compound-containing composition according to [7] and a liquid medium.
  • the article according to [9] which has the surface layer on the surface of a member that constitutes the surface of the touch panel that is touched by the finger.
  • the fluorine-containing compound or the fluorine-containing compound of any one of [1] to [6] is treated by a dry coating method using the fluorine-containing compound-containing composition of [7].
  • a method for producing an article comprising forming a surface layer formed from the composition containing a fluorine-containing compound on the surface of the substrate.
  • the coating liquid of [8] is applied to the surface of the substrate by the wet coating method and dried to form a surface layer formed from the fluorine-containing compound or the fluorine-containing compound-containing composition on the surface of the substrate.
  • a method for manufacturing an article comprising:
  • a fluorine-containing compound which is a compound represented by the following formula (2A) or a compound represented by the following formula (2B).
  • [R f ⁇ ] a1 Q 10 [—CH ⁇ CH 2 ] b1 ...
  • [CH 2 CH-] b2
  • [-CH CH 2 ] b2
  • R f is a fluoroalkyl group (provided that at least one fluorine atom is bonded to the terminal carbon atom on the Q 10 and Q 20 side) or a carbon-carbon atom of a fluoroalkyl group having 2 or more carbon atoms.
  • Q f represents a fluoroalkylene group (provided that at least one fluorine atom is bonded to the terminal carbon atom on the Q 20 side), or —O between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms.
  • Q 10 is an a1+b1 valent linking group having a site in which two or more polar groups are bonded in series via a divalent organic group having 1 to 20 carbon atoms
  • Q 20 is an a2+b2+1 valent linking group having a site in which two or more polar groups are connected in series via a divalent organic group having 1 to 20 carbon atoms
  • the two Q 20 are the same.
  • the polar group is C(O)NH, NHC(O), NH, NHC(O)NH, NHC(S)NH, S(O) 2 NH, NHS(O) 2 , C(O), C( OH), C(OR 4 ), P(O), S(O), C[OP(O)(OR 4 ) 2 ], C[OS(O) 2 R 4 ] and C[OC(O)R. 4 ] (wherein R 4 is an alkyl group) is a polar group selected from the group consisting of: a1 is an integer of 1 or more, a2 is an integer of 0 or more, and R f of 2 or more may be the same or different, b1 and b2 are each an integer of 1 or more. [14] The fluorine-containing compound according to [13], wherein the polar group is C(O)NH, NHC(O), S(O) 2 NH or NHS(O) 2 .
  • the fluorine-containing compound of the present invention it is possible to form a surface layer having excellent fingerprint stain removability and abrasion resistance.
  • a surface layer having excellent fingerprint stain removability and abrasion resistance can be formed.
  • a coating liquid of the present invention a surface layer having excellent fingerprint stain removability and abrasion resistance can be formed.
  • the article of the present invention has a surface layer having excellent fingerprint stain removability and abrasion resistance. According to the method for producing an article of the present invention, an article having a surface layer having excellent fingerprint stain removability and abrasion resistance can be produced.
  • the compound represented by the formula (1A) is referred to as the compound (1A).
  • the group represented by the formula (g1a) is referred to as a group (g1a).
  • the groups represented by other formulas will be described in the same manner.
  • the chemical formula of the oxyfluoroalkylene unit shall be represented by describing its oxygen atom on the left side of the fluoroalkylene group.
  • Reactive silyl group is a general term for hydrolyzable silyl groups and silanol groups (Si—OH).
  • the reactive silyl group is, for example, T(-Si(R) 3-c (L) c ) in formula (1A) or formula (1B).
  • the “hydrolyzable silyl group” means a group capable of undergoing a hydrolysis reaction to form a silanol group.
  • Surface layer means a layer formed on the surface of a substrate.
  • the terminal group include R f1 in formula (g1a) and T in formula (1A) and formula (1B).
  • the fluorine-containing compound is a fluorine-containing compound having a single chain length of a fluorine-containing organic group (R f or Q f )
  • the “molecular weight” of the fluorine-containing organic group is 1 H-NMR and 19 F-NMR. It is a molecular weight calculated by determining the structure of R f .
  • the fluorine-containing compound of the present invention connects a monovalent or divalent fluorine-containing organic group, a reactive silyl group, and a fluorine-containing organic group with a reactive silyl group. It has a specific linking group. That is, the compound may be a compound having a structure of "monovalent fluorine-containing organic group-linking group-reactive silyl group", and "reactive silyl group-linking group-divalent fluorine-containing organic group” It may be a compound having a structure of "linking group-reactive silyl group”.
  • This compound has a fluorine-containing organic group.
  • the present compound having a fluorine-containing organic group is excellent in removing fingerprint stains on the surface layer.
  • the compound has a reactive silyl group at least at one end. Since the present compound having a reactive silyl group at the terminal chemically bonds strongly to the base material, the surface layer has excellent abrasion resistance. Further, as the present compound, a compound having a reactive silyl group only at one end is preferable. A compound having a reactive silyl group only at one end is less likely to aggregate, so that the appearance of the surface layer is excellent. Also, the surface layer has excellent abrasion resistance and fingerprint stain removability.
  • Examples of the monovalent fluorine-containing organic group include a fluoroalkyl group and a monovalent fluoropolyether chain.
  • Examples of the divalent fluorine-containing organic group include a fluoroalkylene group and a divalent fluoropolyether chain.
  • the fluoropolyether chain is a group having a plurality of —O— between carbon-carbon atoms of the fluoroalkyl group. Fluoropolyether chains usually have oxyfluoroalkylene units.
  • a fluoropolyether chain is preferable because the surface layer is more excellent in removing fingerprint stains.
  • As the fluorine-containing organic group a perfluoropolyether chain is more preferable because the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent.
  • the molecular weight of the fluorine-containing organic group is preferably 50 to 1000, more preferably 100 to 900, and particularly preferably 200 to 800, from the viewpoint of achieving both fingerprint stain removability and slip resistance of the surface layer.
  • the molecular weight of the fluorine-containing organic group is at least the lower limit value of the above range, the fingerprint stain removability of the surface layer will be further excellent.
  • the molecular weight of the fluorinated organic group is at most the upper limit value of the above range, the slip resistance of the surface layer will be further excellent.
  • the molecular weight of the fluorine-containing organic group is preferably 1500 to 10000, more preferably 2000 to 8000, and particularly preferably 2500 to 6000, from the viewpoint that the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent.
  • the molecular weight of the fluorine-containing organic group is at least the lower limit value of the above range, the abrasion resistance and fingerprint stain removability of the surface layer are further excellent.
  • the molecular weight of the fluorine-containing organic group is at most the upper limit value of the above range, the abrasion resistance of the surface layer will be further excellent.
  • the reactive silyl group is a group in which one or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom.
  • the hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, the hydrolyzable silyl group becomes a silanol group (Si—OH) by the hydrolysis reaction.
  • the silanol group further undergoes a dehydration condensation reaction between molecules to form a Si—O—Si bond. Further, the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (base material-OH) on the surface of the base material to form a chemical bond (base material-O-Si).
  • Examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group and an isocyanate group.
  • an alkoxy group an alkoxy group having 1 to 6 carbon atoms is preferable.
  • the aryloxy group is preferably an aryloxy group having 3 to 10 carbon atoms.
  • the aryl group of the aryloxy group includes a heteroaryl group.
  • the halogen atom is preferably a chlorine atom.
  • As the acyl group an acyl group having 1 to 6 carbon atoms is preferable.
  • the acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.
  • an alkoxy group and a halogen atom are preferable from the viewpoint of easy production of the present compound.
  • an alkoxy group having 1 to 4 carbon atoms is preferable from the viewpoint of less outgas at the time of application and excellent storage stability of the present compound, and when long-term storage stability of the present compound is required
  • An ethoxy group is particularly preferable, and a methoxy group is particularly preferable when the reaction time after coating is short.
  • the linking group is a group having a site in which two or more polar groups are bonded in series via a divalent organic group having 1 to 20 carbon atoms (hereinafter, also referred to as “polar site E”).
  • polar group and polar group are bonded in series means that the polar group and the polar group do not have a specific branched chain.
  • the specific branched chain means a chain having a fluorine-containing organic group or a reactive silyl group in the chain.
  • the linking group has a branch point P or P′ described later, it means that a polar moiety E is provided between the fluorine-containing organic group and the branch point P.
  • the polar group itself may be the branch point P or P′.
  • Polar groups include C(O)NH, NHC(O), NH, NHC(O)NH, NHC(S)NH, S(O) 2 NH, NHS(O) 2 , C(O), C(OH ), C(OR 4 ), P(O), S(O), C[OP(O)(OR 4 ) 2 ], C[OS(O) 2 R 4 ], and C[OC(O)R 4 ]
  • R 4 is an alkyl group.
  • the alkyl group preferably has 1 to 3 carbon atoms, and 1 is particularly preferable.
  • the linking group may have two or more types of the polar groups.
  • the polar group is classified into a group I having —NH— and a group II other than this.
  • a group II other than this.
  • C(O)NH, NHC(O), S(O), S(O)NH, NHC(O), S(O) ) 2 NH and NHS(O) 2 are preferred, and C(O)NH and NHC(O) are particularly preferred.
  • NHC(O)NH and NHC(S)NH are preferable, and NHC(O)NH is particularly preferable, from the viewpoint that the slip resistance of the surface layer is further excellent.
  • Examples of the divalent organic group to be combined with the polar group I include divalent aliphatic hydrocarbon groups (alkylene group, cycloalkylene group, etc.), divalent aromatic hydrocarbon groups (phenylene group, etc.), A combination thereof and the like can be mentioned, and a divalent aliphatic hydrocarbon group is preferable, and an alkylene group is particularly preferable.
  • the alkylene group may be linear or branched, and is preferably linear.
  • the divalent aliphatic hydrocarbon group may have a substituent (thiol group, thioether group, phenyl group, pyrrolidine group, indolyl group, halogen atom, etc.).
  • the divalent aromatic hydrocarbon group may have a substituent (alkyl group, hydroxyl group, halogen atom, etc.).
  • the carbon number of the divalent organic group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 or 2.
  • a group obtained by removing an amino group and a carboxy group from an amino acid is preferable from the viewpoint of easy production of the present compound.
  • the amino acid glycine and ⁇ -alanine are preferable from the viewpoint of easy production of the present compound and the further excellent abrasion resistance and slip resistance of the surface layer.
  • the number of polar groups in the polar moiety E having a polar group of Group I is preferably as large as possible from the viewpoint that the abrasion resistance of the surface layer is further excellent, and is 2 to 5 from the viewpoint of easy production of the present compound. Preferred is 2 or 3, and particularly preferred.
  • Examples of the polar moiety E having a polar group of group I include the following.
  • Q 4 is a divalent organic group.
  • the carbon number of Q 4 is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 or 2.
  • the carbon number of Q 4 is 1, the polar site E is derived from glycine, for example.
  • the carbon number of Q 4 is 2, the polar site E is derived from ⁇ -alanine, for example.
  • C[OP(O)(OR 4 ) 2 ] and C[OS(O) 2 R 4 ] are preferable, since the surface layer is more excellent in abrasion resistance and slip resistance.
  • C[OP(O)(OR 4 ) 2 ] is particularly preferred.
  • the divalent organic group to be combined with the polar group of Group II include a divalent aliphatic hydrocarbon group (alkylene group, cycloalkylene group, etc.), a divalent aromatic hydrocarbon group (phenylene group, etc.), A combination thereof and the like can be mentioned, and a divalent aliphatic hydrocarbon group is preferable, and an alkylene group is particularly preferable.
  • the alkylene group may be linear or branched, and is preferably linear.
  • the carbon number of the divalent organic group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 or 2.
  • the number of polar groups in the polar moiety E having a polar group of Group II is particularly preferably 2 from the viewpoint of easy production of the present compound.
  • Examples of the polar moiety E having a polar group II are as follows.
  • Q 4 is a divalent organic group.
  • the compound (1A) and the compound (1B) are preferable because the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent.
  • the compound (1A) and the compound (1B) are also collectively referred to as the compound (1).
  • R f is a fluoroalkyl group (provided that at least one fluorine atom is bonded to the terminal carbon atom on the Q 1 and Q 2 side) or a carbon-carbon of a fluoroalkyl group having 2 or more carbon atoms.
  • a group having —O— between atoms (provided that at least one fluorine atom is bonded to the terminal carbon atom on the Q 1 and Q 2 side).
  • Q f represents a fluoroalkylene group (provided that at least one fluorine atom is bonded to the terminal carbon atom on the Q 2 side), or —O between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms.
  • Q 1 is an a1+b1 valent linking group having a site in which two or more polar groups are bonded in series via a divalent organic group having 1 to 20 carbon atoms.
  • Q 2 is an a2+b2+1 valent linking group having a site in which two or more polar groups are bonded in series via a divalent organic group having 1 to 20 carbon atoms, and the two Q 2 are the same. May also be different.
  • the polar group includes C(O)NH, NHC(O), NH, NHC(O)NH, NHC(S)NH, S(O) 2 NH, NHS(O) 2 , C(O), C( OH), C(OR 4 ), P(O), S(O), C[OP(O)(OR 4 ) 2 ], C[OS(O) 2 R 4 ] and C[OC(O)R.
  • R 4 is an alkyl group
  • R 4 is a polar group selected from the group consisting of: T is —Si(R) 3-c (L) c
  • R is an alkyl group
  • L is a hydrolyzable group or a hydroxyl group
  • c is 2 or 3
  • a1 is an integer of 1 or more
  • a2 is an integer of 0 or more
  • R f of 2 or more may be the same or different.
  • b1 and b2 are each an integer of 1 or more, and Ts of 2 or more may be the same or different.
  • the compound (1A) has R f at the terminal.
  • the compound (1A) having R f at the terminal is excellent in removing fingerprint stains on the surface layer.
  • the compound (1B) has Q f .
  • the compound (1B) having Q f is excellent in removing fingerprint stains on the surface layer.
  • the compound (1) has a reactive silyl group at the terminal.
  • the compound (1) having a reactive silyl group at the terminal has a strong chemical bond with the base material, and thus has excellent abrasion resistance of the surface layer.
  • the compound (1A) which is a compound having a reactive silyl group only at one terminal, is excellent in the appearance of the surface layer because it is less likely to aggregate, as compared with the compound (1B). It is more preferable because it is excellent in abrasion resistance and fingerprint stain removability.
  • a1 is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2 from the viewpoint of easy production of the compound (1A) and further excellent abrasion resistance and fingerprint stain removability of the surface layer. .
  • R f of 2 or more are the same.
  • a2 is preferably 0 to 6, more preferably 0 to 4, and particularly preferably 0 to 2 from the viewpoint of easy production of the compound (1B) and the further excellent abrasion resistance and fingerprint stain removability of the surface layer.
  • a2 is 1 or more, it is preferable that two or more R f contained in the compound (1B) are the same.
  • b1 is preferably 1 to 6, more preferably 1 to 5, and still more preferably 1 to 4 from the viewpoint of easy production of the compound (1A) and further excellent abrasion resistance and fingerprint stain removability of the surface layer. 2 to 4 are particularly preferable. Further, when b1 is 2 or more, it is preferable that Ts of 2 or more are the same. b2 is preferably 1 to 6, more preferably 1 to 5, and further preferably 1 to 4 from the viewpoint that the compound (1B) can be easily produced and that the surface layer is more excellent in abrasion resistance and fingerprint stain removability. 2 to 4 are particularly preferable. Further, two or more T's contained in the compound (1B) are preferably the same. Further, in the compound (1B), it is preferable that two [T-] b2 [R f -] a2 Q 2- bonded to Q f are the same group from the viewpoint of easy production thereof.
  • R f is a monovalent fluorine-containing organic group.
  • a fluoropolyether chain is preferable because the fingerprint stain removability of the surface layer is further excellent.
  • R f a perfluoropolyether chain is more preferable because the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent.
  • Q f is a divalent fluorine-containing organic group.
  • a fluoropolyether chain is preferable because the surface layer is more excellent in removing fingerprint stains.
  • a perfluoropolyether chain is more preferable because the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent.
  • the preferable range of the molecular weight of R f and Q f is the same as the preferable range of the molecular weight of the above-mentioned fluorine-containing organic group.
  • R f examples include a group (g1a).
  • R f1 is a fluoroalkyl group having 1 to 6 carbon atoms (however, when m is 0, at least one fluorine atom is bonded to the terminal carbon atom on the Q 1 or Q 2 side).
  • R f2 is a fluoroalkylene group having 1 to 6 carbon atoms (provided that at least one fluorine atom is attached to the Q 1 or Q 2 side terminal carbon atom of R f2 which bind to Q 1 or Q 2 .), m is an integer of 0 or more, and when m is 2 or more, (OR f2 ) m may be composed of two or more kinds of OR f2 .
  • Q f examples include a group having a group (g1b). -R f2 (OR f2 ) m' -... (g1b)
  • R f2 is a fluoroalkylene group having 1 to 6 carbon atoms (provided that at least one fluorine atom is bonded to the terminal carbon atom on the Q 1 or Q 2 side), and m′ is 1 It is the above integer, and when m′ is 2 or more, (OR f2 ) m′ may be composed of two or more kinds of OR f2 .
  • R f1 When R f1 has 1 to 6 carbon atoms, the surface layer is more excellent in abrasion resistance and fingerprint stain removability.
  • the carbon number of the fluoroalkyl group of R f1 is preferably 1 to 4 and particularly preferably 1 to 3 from the viewpoint that the abrasion resistance and fingerprint stain removability of the surface layer are further excellent.
  • R f1 is preferably a perfluoroalkyl group from the viewpoint that the surface layer is more excellent in abrasion resistance and fingerprint stain removability.
  • the terminal In the compound (1A) in which R f1 is a perfluoroalkyl group, the terminal is CF 3 ⁇ .
  • R f1 includes 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 —, CF 3 CF(CF 3 )— and the like.
  • R f2 When the carbon number of R f2 is 1 to 6, the abrasion resistance and fingerprint stain removability of the surface layer are further excellent.
  • R f2 a linear fluoroalkylene group is preferable because the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent.
  • R f2 a perfluoroalkylene group is preferable because the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent.
  • the proportion of perfluoroalkylene groups in the total R f2 is preferably 60 mol% or more, more preferably 80 mol% or more, and particularly preferably 100 mol% from the viewpoint that the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent. preferable.
  • m is preferably an integer of 0 to 30, more preferably an integer of 0 to 20, and particularly preferably an integer of 0 to 10.
  • m′ is preferably an integer of 1 to 30, more preferably an integer of 1 to 20, and particularly preferably an integer of 1 to 10.
  • m' is not more than the upper limit of the above range, the slip resistance of the surface layer is further excellent.
  • m and m′ are preferably an integer of 2 to 200, more preferably an integer of 5 to 150, particularly preferably an integer of 10 to 100.
  • m and m′ are not less than the lower limit of the above range, the surface layer is more excellent in abrasion resistance and fingerprint stain removability.
  • m and m′ are not more than the upper limit of the above range, the abrasion resistance of the surface layer is further excellent. That is, when the number average molecular weight of the compound (1) is too large, the number of hydrolyzable silyl groups present per unit molecular weight decreases, and the abrasion resistance of the surface layer decreases.
  • OR f2 that is, as the oxyfluoroalkylene unit, OCHF, OCF 2 CHF, OCHFCF 2 , OCF 2 CH 2 , OCH 2 CF 2 , OCF 2 CF 2 CHF, OCHFCF 2 CF 2 , OCF 2 CF 2 CH 2 , OCH 2 CF 2 CF 2, OCF 2 CF 2 CF 2 CH 2, OCH 2 CF 2 CF 2 CF 2, OCF 2 CF 2 CF 2 CH 2, OCH 2 CF 2 CF 2 CF 2 CF 2, OCF 2 CF 2 CF 2 CF 2 CF 2 CH 2, OCH 2 CF 2 CF 2 CF 2 CF 2 CF 2, OCF 2, OCF 2 CF 2, OCF 2 CF 2 CF 2 CF 2, OCF (CF 3) CF 2, OCF 2 CF 2 CF 2 CF 2 CF 2, OCF (CF 3) CF 2 CF 2, OCF 2 CF 2 CF 2 CF 2 CF 2, OCF 2 CF 2 CF 2
  • each OR f2 is not limited.
  • OCF 2 and OCF 2 CF 2 may be arranged in a random, alternating, block.
  • the two or more OR f2 is present, that there are two or more OR f2 having different number of carbon atoms, that the number of hydrogen atoms are present two or more different OR f2, two position of the hydrogen atoms are different the presence of oR f2 above, and, whether or side chain type of side chains may be the same carbon number (number of carbon atoms in the number of side chains or side chains, etc.) is two or more different oR f2 It exists.
  • the structure represented by ⁇ (OCF 2 ) m1 (OCF 2 CF 2 ) m2 ⁇ includes m1 (OCF 2 ) and m2 (OCF 2 CF 2 ).
  • m1, m2, m3, m4, m5, m6, m7, m8 and m9 are integers of 1 or more.
  • the upper limits of m1, m2, m3, m4, m5, m6, m7, m8 and m9 are adjusted according to the upper limit of m.
  • Q 1 is an a1+b1 valent linear or branched linking group.
  • Q 2 is an a2+b2+1 valent linear or branched linking group.
  • Q 1 and Q 2 have the polar moiety E described above.
  • Q 1 is at least one branch point (hereinafter referred to as “branch point P”) selected from the group consisting of C, N, Si, a ring structure and an a1+b1 valent organopolysiloxane residue when a1+b1 is 3 or more. .) is further included.
  • branch point P branch point selected from the group consisting of C, N, Si, a ring structure and an a1+b1 valent organopolysiloxane residue when a1+b1 is 3 or more. .
  • Q 2 is at least one branch point (hereinafter referred to as “branch point P′”) selected from the group consisting of C, N, Si, a ring structure and an a2+b2+1 valent organopolysiloxane residue when a2+b2+1 is 3 or more. It is preferable to have the following).
  • branch point P′ selected from the group consisting of C, N, Si, a ring structure and an a2+b2+1 valent organopolysiloxane residue when a2+b2+1 is 3 or more. It is preferable to have the following).
  • a specific branched chain is bonded to the branch point P'.
  • the ring structure is a 3- to 8-membered aliphatic ring, a 3- to 8-membered ring, from the viewpoint of easy production of the compound (1) and further excellent abrasion resistance, light resistance and chemical resistance of the surface layer.
  • Examples of the a1+b1 valent organopolysiloxane residue or the a2+b2+1 valent organopolysiloxane residue include the following groups.
  • R 5 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the alkyl group and the alkoxy group of R 5 preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.
  • R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • bond B —O— is preferable from the viewpoint of easy production of the compound (1).
  • Examples of the divalent organopolysiloxane residue include groups represented by the following formulae.
  • R 7 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the alkyl group and the alkoxy group of R 7 preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.
  • Q 1 is a combination of two or more divalent hydrocarbon groups, one or more polar moieties E and one or more branch points P, and two or more hydrocarbon groups and one or more polarities. Examples include combinations of the site E, one or more branch points P, and one or more bonds B.
  • Q 1 is a combination of two or more divalent hydrocarbon groups and one or more polar moieties E, and two or more hydrocarbon groups and 1 Combinations of one or more polar moieties E and one or more bonds B are included.
  • Q 2 a combination of two or more divalent hydrocarbon groups, one or more polar moieties E and one or more branch points P′, and two or more hydrocarbon groups and one or more A combination of a polar moiety E, one or more branch points P′ and one or more bonds B can be mentioned.
  • Q 2 is a combination of two or more divalent hydrocarbon groups and one or more polar moieties E, and two or more hydrocarbon groups. Combinations of one or more polar moieties E and one or more bonds B are included.
  • divalent hydrocarbon group examples include a divalent aliphatic hydrocarbon group (alkylene group, cycloalkylene group, etc.) and a divalent aromatic hydrocarbon group (phenylene group, etc.).
  • the carbon number of the divalent hydrocarbon group is preferably 1-10, more preferably 1-6, and particularly preferably 1-4.
  • the A side is connected to R f or Q f , and the Q 22 , Q 23 , Q 24 , Q 25 , Q 26, and Q 27 sides are connected to T.
  • A is a single bond or an alkylene group.
  • E is a site in which two or more polar groups are bonded in series via a divalent organic group having 1 to 20 carbon atoms, and in the formula (g2-7), the polar group at the terminal on the Q 27 side is C(OH), C(OR 4 ), P(O), S(O), C[OP(O)(OR 3 ) 2 ], C[OS(O) 2 R 3 ], or C[OC(O ) R 3 ].
  • Q 11 is a single bond, —O—, an alkylene group, or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms.
  • Q 12 is a single bond or an alkylene group, if Q 1 or Q 2 has a Q 12 2 or more, two or more Q 12 may be different even in the same.
  • Q 13 is an alkylene group.
  • Q 14 is Q 12 when the atom in Z to which Q 14 is bonded is a carbon atom, Q 13 when the atom in Z to which Q 14 is bonded is a nitrogen atom, and Q 1 or Q 2 is Q 14 When 2 or more are included, two or more Q 14's may be the same or different.
  • Q 15 is an alkylene group, if Q 1 or Q 2 has a Q 15 2 or more, two or more Q 15 may be different even in the same.
  • Q 22 is an alkylene group, a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, a group having —O— at an end of the alkylene group which is not connected to Si, or a group having 2 carbon atoms.
  • a group having -O- between the carbon-carbon atoms of the above alkylene group and having -O- at the terminal on the side not connected to Si, and two or more Q 22 s may be the same or different. Good.
  • Q 23 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and two Q 23 may be the same or different.
  • Q 24 is Q 22 when the atom in Z to which Q 24 is bonded is a carbon atom, and is Q 23 when the atom in Z to which Q 24 is bonded is a nitrogen atom, and two or more Q 24 are the same. It may or may not be.
  • Q 25 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and 2 or more Q 25 may be the same or different.
  • Q 26 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms.
  • Q 27 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and two Q 27 may be the same or different.
  • Z is a group having a ring structure of a1+b1 valence or a2+b2+1 having a carbon atom or a nitrogen atom to which Q 14 is directly bonded and a carbon atom or a nitrogen atom to which Q 24 is directly bonded.
  • R 1 is a hydrogen atom or an alkyl group, if Q 1 or Q 2 has the R 1 2 or more, 2 or more of R 1 may be different even in the same.
  • R 2 is a hydrogen atom or an alkyl group, and R 3 is an alkyl group.
  • d1 is an integer of 0 to 3, preferably 1 or 2
  • d2 is an integer of 0 to 3, preferably 1 or 2
  • d1+d2 is an integer of 1 to 3.
  • d3 is an integer of 0 to 3, preferably 1 or 2
  • d4 is an integer of 0 to 3, preferably 1 or 2
  • d3+d4 is an integer of 1 to 3.
  • d1+d3 is an integer of 1 to 5, preferably 2 or 3, and d2+d4 is an integer of 1 to 5, preferably an integer of 2 to 4.
  • e1 is an integer of 1 to 3, preferably 1 or 2
  • e2 is an integer of 1 to 3, preferably 2 or 3, and e1+e2 is 3 or 4.
  • h1 is an integer of 1 or more, preferably 1 or 2, and h2 is an integer of 1 or more, preferably 2 or 3.
  • i1 is an integer of 1 to 3, preferably 1 or 2
  • i2 is an integer of 1 to 3, preferably 2 or 3, and i1+i2 is 3 or 4.
  • the number of carbon atoms of the alkylene group of A is preferably 1 to 5, more preferably 1 to 2, and particularly preferably 1 from the viewpoint of easy production of the compound (1).
  • Examples of E include the polar site E described above, and the preferred forms are also the same.
  • the number of carbon atoms of the alkylene group of Q 11 , Q 12 , Q 13 , Q 14 , Q 15 , Q 22 , Q 23 , Q 24 , Q 25 , Q 26 and Q 27 is such that the compound (1) can be easily produced. Further, from the viewpoint that the abrasion resistance, light resistance and chemical resistance of the surface layer are further excellent, 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is particularly preferable. However, the lower limit of the number of carbon atoms of the alkylene group when it has a specific bond between carbon and carbon atoms is 2.
  • Examples of the ring structure in Z include the ring structures described above, and the preferred forms are also the same. Since Q 14 and Q 24 are directly bonded to the ring structure in Z, for example, an alkylene group is not connected to the ring structure and Q 14 or Q 24 is not connected to the alkylene group.
  • the number of carbon atoms of the alkyl group of R 1 , R 2 and R 3 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of the compound (1).
  • h1 is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 or 2 from the viewpoint that the compound (1) can be easily produced and that the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent. 1 is particularly preferred.
  • h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3 from the viewpoint of easy production of the compound (1) and the further excellent abrasion resistance and fingerprint stain removability of the surface layer. .
  • the Si side is connected to Q 22 , Q 23 , Q 24 , Q 25 , Q 26 and Q 27 , the Q 3 side is connected to T
  • R 8 is an alkyl group
  • Q is 3 is an alkylene group, a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or —(OSi(R 9 ) 2 ) p —O—, and Q 3 of 2 or more is They may be the same or different
  • k is 2 or 3
  • R 9 is an alkyl group, a phenyl group or an alkoxy group, and two R 9 are the same or different.
  • p is an integer of 0 to 5, and when p is 2 or more, (OSi(R 9 ) 2 ) of 2 or more may be the same or different.
  • the number of carbon atoms of the alkylene group of Q 3 is preferably 1 to 10 and more preferably 1 to 6 from the viewpoint of easy production of the compound (1) and the further excellent abrasion resistance, light resistance and chemical resistance of the surface layer. More preferably, 1 to 4 is particularly preferable. However, the lower limit of the number of carbon atoms of the alkylene group when it has a specific bond between carbon and carbon atoms is 2.
  • the number of carbon atoms of the alkyl group of R 8 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of the compound (1).
  • the number of carbon atoms of the alkyl group of R 9 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of the compound (1).
  • the number of carbon atoms of the alkoxy group of R 9 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of excellent storage stability of the compound (1).
  • p is preferably 0 or 1.
  • T is —Si(R) 3-c (L) c, which is a reactive silyl group.
  • the number of carbon atoms of the alkyl group of R is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of the compound (1).
  • Examples of the hydrolyzable group for L include the same as the above-mentioned hydrolyzable groups, and the preferred forms are also the same.
  • c is particularly preferably 3 because the adhesion between the surface layer and the substrate becomes stronger.
  • Plural Ts in the compound (1) may be the same or different. From the viewpoint of easy production of the compound (1), the same group is preferable.
  • Examples of the compound (1) include compounds of the following formula.
  • the compound of the following formula is industrially easy to produce and easy to handle, and the surface layer has water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance, light resistance and chemical resistance. Of these, light resistance is particularly excellent, which is preferable.
  • the R f and Q f in the formula of the compound is the same as R f and Q f in the above-described formula (1A) and the formula (1B), a preferred form same.
  • Examples of the compound (1A) in which Q 1 is the group (g2-1) include compounds of the following formulas.
  • Examples of the compound (1A) in which Q 1 is the group (g2-2) include the compounds of the following formulas.
  • Examples of the compound (1A) in which Q 1 is the group (g2-3) include compounds of the following formulas.
  • Examples of the compound (1A) in which Q 1 is the group (g2-4) include the compounds of the following formulas.
  • Examples of the compound (1A) in which Q 1 is the group (g2-6) include the compounds of the following formulas.
  • Examples of the compound (1A) in which Q 1 is the group (g2-7) include compounds of the following formulae.
  • Examples of the compound (1A) in which Q 1 is the group (g2-9) include compounds of the following formulas.
  • Examples of the compound (1B) in which Q 2 is the group (g2-1) include compounds of the following formulas.
  • Examples of the compound (1B) in which Q 2 is the group (g2-2) include compounds of the following formulas.
  • Examples of the compound (1B) in which Q 2 is the group (g2-3) include the compounds of the following formulas.
  • Examples of the compound (1B) in which Q 2 is the group (g2-4) include the compounds of the following formulas.
  • Examples of the compound (1B) in which Q 2 is the group (g2-6) include the compounds of the following formulae.
  • Examples of the compound (1B) in which Q 2 is the group (g2-7) include compounds of the following formulas.
  • Examples of the compound (1B) in which Q 2 is the group (g2-9) include compounds of the following formulas.
  • Compound (1A) can be produced, for example, by a method in which compound (2A) and compound (3a) or compound (3b) are hydrosilylated.
  • Compound (1B) can be produced, for example, by a method in which compound (2B) and compound (3a) or compound (3b) are hydrosilylated. [R f ⁇ ] a1 Q 10 [—CH ⁇ CH 2 ] b1 ...
  • Q 20 is an a2+b2+1-valent linking group having a site in which two or more polar groups are bonded in series via a divalent organic group having 1 to 20 carbon atoms, and two Q 2 20 may be the same or different and symbols other than Q 20 are the same as the sign in the formula (1B).
  • Q 10 [—CH ⁇ CH 2 ] b1 becomes Q 1 in the compound (1A) after hydrosilylation.
  • Examples of Q 10 include the same groups as Q 1, and preferred forms are also the same.
  • Q 20 [—CH ⁇ CH 2 ] b2 becomes Q 2 in the compound (1B) after hydrosilylation.
  • Examples of Q 20 include the same groups as Q 2, and preferred forms are also the same.
  • Q 220 is an alkylene group, a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, a group having —O— at the terminal of the alkylene group which is not connected to Si, or carbon.
  • a group having -O- between carbon-carbon atoms of an alkylene group of 2 or more and having -O- at the terminal not connected to Si, and 2 or more of Q 220 may be the same or different.
  • Q 230 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and two or more Q 230 may be the same or different.
  • Q 240 is Q 220 when the atom in Z to which Q 240 is bonded is a carbon atom, and Q 230 when the atom in Z to which Q 240 is bonded is a nitrogen atom, and two or more Q 240 are the same. It may or may not be.
  • Q 250 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and 2 or more Q 250 may be the same or different.
  • Q 260 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms.
  • Q 270 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and two Q 270 may be the same or different.
  • Codes other than Q 220 , Q 230 , Q 240 , Q 250 , Q 260, and Q 270 are the same as those in formulas (g2-1) to (g2-7).
  • Q 220 -CH CH 2 becomes Q 22 in the compound (1) after hydrosilylation.
  • Q 220 include the same groups as Q 22, and preferred forms are also the same.
  • Q 230 CH ⁇ CH 2 becomes Q 23 in the compound (1) after hydrosilylation.
  • Q 230 include the same groups as Q 23, and preferred forms are also the same.
  • Q 240 CH ⁇ CH 2 becomes Q 24 in the compound (1) after hydrosilylation.
  • Q 240 include the same groups as Q 24, and the preferred forms are also the same.
  • Q 250 include the same groups as Q 25, and preferred forms are also the same.
  • Q 260 CH ⁇ CH 2 becomes Q 26 in the compound (1) after hydrosilylation.
  • Q 260 examples include the same groups as Q 26, and preferred forms are also the same.
  • Q 270 -CH CH 2 is a Q 27 in after the hydrosilylation compound (1).
  • Examples of Q 270 include the same groups as Q 27, and preferred forms are also the same.
  • G 1 is a group (g5), and two or more G 1 s that Q 10 [—CH ⁇ CH 2 ] b1 or Q 20 [—CH ⁇ CH 2 ] b2 have are the same or different.
  • the symbols other than G 1 are the same as the symbols in the formulas (g2-1) to (g2-7).
  • Q 30 is an alkylene group or a group having —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and 2 or more Q 30 may be the same or different
  • Codes other than Q 30 are the same as the codes in the formula (g3).
  • Q 30 —CH ⁇ CH 2 becomes Q 3 in the group (g3) after hydrosilylation.
  • Examples of Q 30 include the same groups as Q 3 (provided that —(OSi(R 9 ) 2 ) p —O— is excluded.), and preferred forms are also the same.
  • Compound (2A) can be produced, for example, by the following procedure when polar site E is —C(O)NH—Q 4 —C(O)NH—.
  • amino-protecting group examples include a tert-butoxycarbonyl group (Boc), a benzyloxycarbonyl group, a 9-fluorenyloxycarboxy group, a 2,2,2-trichloroethoxycarbonyl group, an allyloxycarbonyl group, an acetyl group, Examples thereof include benzoyl group and benzyl group.
  • Compound (4A) is available as a commercially available compound.
  • compound (4A) can be produced, for example, by the method described in Patent Document 1 or the method described in International Publication No. 2019/039186.
  • the compound (5) is available, for example, as a commercially available N-protected amino acid (N-Boc-glycine, N-Boc- ⁇ -alanine, etc.).
  • R f -C(O)-X (8a) [R f -C(O)NH-Q 4 -C(O)NH-] a1 Q 100 [-CH CH 2 ] b1 ...(2Aa)
  • X is a halogen atom, an alkoxy group, or a hydroxyl group, and symbols other than X are the same as the symbols in Formula (2A).
  • the compound (8a) can be produced, for example, by the method described in WO 2009/008380, the method described in WO 2013/121984, the method described in WO 2013/121986, or WO 2015/087902. In WO2017/038830, in WO2017/038832, in WO2018/143433, in WO2018/216630. It can be produced by the described method.
  • the compound (2A) in which the polar moiety E is other than —C(O)NH—Q 4 —C(O)NH— can be produced, for example, by the method described in Examples.
  • the compound (2B) can be produced, for example, by the following procedure.
  • the compound (4B) and the compound (5) are subjected to an amidation reaction to obtain the compound (6B).
  • H 2 NQ 200 [-CH CH 2 ] b2 ...
  • Pro-NH-Q 4 -C(O)NH-Q 200 [-CH CH 2 ] b2 ...
  • Q 200 is a group obtained by removing the polar moiety E from Q 20 , Pro is a protecting group for an amino group, Q 4 is a divalent organic group, and symbols other than Pro and Q 4 are , which is the same as the sign in Expression (2B).
  • the compound (7B) and the compound (8b) are subjected to an amidation reaction to obtain the compound (2Ba).
  • X is a halogen atom, an alkoxy group, or a hydroxyl group, and the symbols other than X are the same as the symbols in Formula (2B) and Formula (6B).
  • Compound (8b) can be produced by the same method as for compound (8a).
  • a surface layer having excellent abrasion resistance and fingerprint stain removability can be formed for the following reasons. Since the compound (1) has the polar moiety E, it is easily crosslinked between molecules by intermolecular interaction (hydrogen bond or dipole interaction). Therefore, also in the surface layer, the compounds (1) bonded to the substrate are crosslinked. Therefore, the compound (1) is likely to remain in the surface layer even if the bonding portion derived from the reactive silyl group with the substrate is cleaved. Therefore, the surface layer has excellent abrasion resistance and fingerprint stain removability.
  • the fluorine-containing compound-containing composition of the present invention contains at least one compound (1) and another fluorine-containing compound.
  • fluorine-containing compound a fluorine-containing compound that is by-produced in the production process of compound (1) (hereinafter, also referred to as “by-product fluorine-containing compound”) and a known compound used for the same purpose as compound (1) Examples thereof include fluorine-containing compounds.
  • by-product fluorine-containing compound a fluorine-containing compound that is by-produced in the production process of compound (1)
  • the other fluorine-containing compound a compound that is less likely to deteriorate the characteristics of the compound (1) is preferable.
  • Examples of the by-product fluorine-containing compound include unreacted compound (2A) or compound (2B), and a fluorine-containing compound in which a part of the allyl group is isomerized to an inner olefin during hydrosilylation in the production of compound (1).
  • Examples of known fluorine-containing compounds include fluorine-containing compounds that are commercially available as surface treatment agents. When the composition contains a known fluorine-containing compound, a new action effect such as supplementing the characteristic (1) may be exhibited.
  • the content of the compound (1) is preferably 60% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, and particularly preferably 80% by mass or more and less than 100% by mass.
  • the content of the other fluorine-containing compound is preferably more than 0 mass% and 40 mass% or less, more preferably more than 0 mass% and 30 mass% or less, particularly preferably more than 0 mass% and 20 mass% or less. ..
  • the total content of the compound (1) and the content of other fluorine-containing compounds is preferably 80 to 100% by mass, and particularly preferably 85 to 100% by mass in the present composition.
  • the present composition may contain components other than the compound (1) and other fluorine-containing compounds as long as the effects of the present invention are not impaired.
  • Other components include (1) and by-products (however, by-product fluorine-containing compounds are excluded) generated in the known production process of fluorine-containing compounds, unreacted raw materials, and other inevitable compounds in production. ..
  • Other components include additives such as acid catalysts and basic catalysts that accelerate the hydrolysis and condensation reaction of the hydrolyzable silyl group.
  • the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like.
  • the basic catalyst include sodium hydroxide, potassium hydroxide, ammonia and the like.
  • the content of the other components is preferably 0 to 9.999% by mass, and particularly preferably 0 to 0.99% by mass in the composition.
  • the coating liquid of the present invention contains the compound (1) or the present composition and a liquid medium.
  • the coating liquid may be a solution or a dispersion liquid.
  • the liquid medium is preferably an organic solvent.
  • the organic solvent may be a fluorine-containing organic solvent or a non-fluorine organic solvent, or may include both solvents.
  • the fluorine-containing organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines and fluoroalcohols.
  • As the fluorinated alkane a compound having 4 to 8 carbon atoms is preferable.
  • Examples of commercially available products include C 6 F 13 H (manufactured by AGC, Asahiclin (registered trademark) AC-2000), C 6 F 13 C 2 H 5 (manufactured by AGC, Asahiclin (registered trademark) AC-6000), C 2 F 5 CHFCHFCF 3 (Kemazu Co., Vertrel (R) XF) and the like.
  • Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis(trifluoromethyl)benzene and the like.
  • As the fluoroalkyl ether a compound having 4 to 12 carbon atoms is preferable.
  • CF 3 CH 2 OCF 2 CF 2 H manufactured by AGC, ASAHIKLIN (registered trademark) AE-3000
  • C 4 F 9 OCH 3 manufactured by 3M, Novec (registered trademark) 7100
  • C. 4 F 9 OC 2 H 5 3M Co., Novec (TM) 7200
  • C 2 F 5 CF OH 3 C 3 F 7 (3M Co., Novec (TM) 7300)
  • fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
  • the fluoroalcohol examples include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol and hexafluoroisopropanol.
  • the non-fluorine organic solvent is preferably a compound containing only hydrogen atoms and carbon atoms and a compound containing only hydrogen atoms, carbon atoms and oxygen atoms, and examples thereof include hydrocarbons, alcohols, ketones, ethers and esters.
  • the liquid medium may be a mixed medium in which two or more kinds are mixed.
  • the content of the compound (1) or the present composition is preferably 0.001 to 10% by mass, and particularly preferably 0.01 to 1% by mass in the present coating liquid.
  • the content of the liquid medium in the coating liquid is preferably 90 to 99.999% by mass, and particularly preferably 99 to 99.99% by mass.
  • the article of the present invention (hereinafter, also referred to as “the article”) has a surface layer formed from the compound (1) or the composition on the surface of a substrate.
  • the surface layer may be formed on a part of the surface of the base material or may be formed on the entire surface of the base material.
  • the surface layer may be spread like a film on the surface of the substrate, or may be scattered in dots.
  • the surface layer contains the compound (1) in a state where a part or all of the hydrolyzable silyl groups of the compound (1) are hydrolyzed and the silanol groups are dehydrated and condensed.
  • the thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. When the thickness of the surface layer is 1 nm or more, the effect of the surface treatment is likely to be sufficiently obtained. When the thickness of the surface layer is 100 nm or less, the utilization efficiency is high.
  • the thickness of the surface layer is calculated from the vibration period of the interference pattern by obtaining the interference pattern of the reflected X-ray by the X-ray reflectance method using an X-ray diffractometer for thin film analysis (RIGAKU, ATX-G). it can.
  • the base material examples include base materials that are required to have water and oil repellency. For example, place it on another article (such as a stylus) or a substrate that may be used by touching the human fingers, a substrate that may be held by the human fingers during operation, or another article (such as a mounting table). There are occasional base materials. Examples of the material of the base material include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened. A base film such as a SiO 2 film may be formed on the surface of the base material. As the base material, a base material for a touch panel, a base material for a display and a spectacle lens are suitable, and a base material for a touch panel is particularly suitable.
  • glass or transparent resin is preferable.
  • a glass or a resin film used for an exterior portion (excluding the display portion) of a device such as a mobile phone (for example, a smartphone), a mobile information terminal (for example, a tablet terminal), a game machine, a remote controller is also preferable.
  • the present article can be produced, for example, by the following method.
  • dry coating methods include vacuum deposition, CVD, and sputtering.
  • the vacuum deposition method is preferable from the viewpoint of suppressing the decomposition of the compound (1) and the simplicity of the apparatus.
  • a pellet-like substance obtained by impregnating a porous metal body such as iron or steel with the compound (1) or the present composition may be used.
  • a pellet-like substance impregnated with the compound (1) or the present composition may be used by impregnating the coating liquid with a porous metal such as iron or steel and drying the liquid medium.
  • Wet coating methods include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir-Blodgett method, gravure method.
  • a coating method and the like can be mentioned.
  • Example 1 (Example 1-1) 2.1 g of acetonitrile and 500 mL of tetrahydrofuran (hereinafter, also referred to as “THF”) were added to a 1000 mL four-necked flask, and the mixture was stirred under a nitrogen atmosphere while cooling with a dry ice-acetone bath. Thereafter, 50 mL of a hexane solution of lithium diisopropylamide (1.1 mol/L, manufactured by Aldrich) was added, and then 7.5 g of allyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The contents in the flask were stirred while returning to 25°C.
  • THF tetrahydrofuran
  • Example 1-2 To a 100 mL eggplant-shaped flask, 3.0 g (9.3 mmol) of the compound (6-1) obtained in Example 1-1 and 50 mL of dichloromethane were added and stirred under ice cooling. 10.6 g (93 mmol) of trifluoroacetic acid was added, and the mixture was stirred at 25°C for 1.5 hours. A 10% aqueous sodium hydroxide solution was added to the obtained solution to make the solution basic, and then extraction operation was performed using dichloromethane. 1.8 g of the compound (7-1) was obtained.
  • Example 1-4 A compound (1-1) was obtained in the same manner as in Example 11-3 of Patent Document 2, except that the compound (2-1) obtained in Example 1-3 was used.
  • Example 2 A compound (1-2) was obtained in the same manner as in Example 1 except that the compound (7-1) obtained in Example 1-2 was used instead of the compound (4-1) in Example 1-1.
  • Example 3 Compound (7- was prepared in the same manner as in Example 1-1 and Example 1-2, except that compound (5-2) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of compound (5-1) in Example 1-1. 3) was obtained.
  • Example 3-2 Compound (1-) was obtained in the same manner as in Example 1-3 and Example 1-4, except that compound (7-3) obtained in Example 3-1 was used instead of compound (7-1) in Example 1-3. 3) was obtained.
  • Example 4 A compound (1-4) was obtained in the same manner as in Example 1 except that the compound (7-3) obtained in Example 3-1 was used instead of the compound (4-1) in Example 1-1.
  • Example 5 (Example 5-1) Compound (7-5) was obtained in the same manner as in Example 1-1 and Example 1-2, except that compound (4-2) was used instead of compound (4-1) in Example 1-1.
  • Example 5-2 Compound (1-) was obtained in the same manner as in Example 1-3 and Example 1-4, except that compound (7-5) obtained in Example 5-1 was used instead of compound (7-1) in Example 1-3. 5) was obtained.
  • Example 6 A compound (1-6) was obtained in the same manner as in Example 1 except that the compound (7-5) obtained in Example 5-1 was used instead of the compound (4-1) in Example 1-1.
  • Example 7 Example 7-1 and Example except that the compound (4-2) was used instead of the compound (4-1) and the compound (5-2) was used instead of the compound (5-1) in Example 1-1.
  • Compound (7-7) was obtained in the same manner as 1-2.
  • Example 7-2 The compound (1-) was prepared in the same manner as in Example 1-3 and Example 1-4, except that the compound (7-7) obtained in Example 7-1 was used instead of the compound (7-1) in Example 1-3. 7) was obtained.
  • Example 8 A compound (1-8) was obtained in the same manner as in Example 1 except that the compound (7-7) obtained in Example 7-1 was used instead of the compound (4-1) in Example 1-1.
  • Example 9 Compound (4-3) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used instead of compound (4-1) in Example 1-1, in the same manner as in Example 1-1 and Example 1-2. 7-9) was obtained.
  • Example 9-2 Compound (1-) was obtained in the same manner as in Example 1-3 and Example 1-4, except that compound (7-9) obtained in Example 9-1 was used instead of compound (7-1) in Example 1-3. 9) was obtained.
  • Example 10 A compound (1-10) was obtained in the same manner as in Example 1 except that the compound (7-9) obtained in Example 9-1 was used instead of the compound (4-1) in Example 1-1.
  • Example 11 Example 1-1 and Example except that the compound (4-3) was used instead of the compound (4-1) in Example 1-1 and the compound (5-2) was used instead of the compound (5-1) Compound (7-11) was obtained in the same manner as 1-2.
  • Example 11-2 Compound (1-) was prepared in the same manner as in Example 1-3 and Example 1-4, except that compound (7-11) obtained in Example 11-1 was used instead of compound (7-1) in Example 1-3. 11) was obtained.
  • Example 12 A compound (1-12) was obtained in the same manner as in Example 1 except that the compound (7-11) obtained in Example 11-1 was used instead of the compound (4-1) in Example 1-1.
  • Example 13 (Example 13-1) In a 50 mL round-bottomed flask, 10.0 g of the compound (2-1) obtained in Example 1-3 and 20 mL of AC-2000 were placed, and after cooling with ice, a solution of lithium aluminum hydride in THF (2.5 mol/L , Manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise. After the temperature was raised to 60 degrees, it was stirred for 12 hours. From NMR, it was confirmed that all the compound (2-1) was converted to the compound (2-13). The resulting solution was ice-cooled, 2 g of sodium sulfate decahydrate was added, the mixture was stirred for 1 hour, and filtered to obtain 6.7 g of compound (2-13).
  • THF lithium aluminum hydride in THF
  • Example 13-2 Compound (1-13) was obtained in the same manner as in Example 1-4, except that compound (2-13) obtained in Example 13-1 was used instead of compound (2-1).
  • Example 14 (Example 14-1) A 50 mL eggplant-shaped flask was charged with 10.0 g of the compound (2-2) obtained in the middle of Example 2 and 20 mL of AC-2000, and the mixture was ice-cooled, and then a lithium aluminum hydride solution in THF (2.5 mol/L was added). ) Was added dropwise. After the temperature was raised to 60 degrees, it was stirred for 12 hours. From NMR, it was confirmed that all the compound (2-2) was converted to the compound (2-14). The resulting solution was ice-cooled, 4 g of sodium sulfate decahydrate was added, the mixture was stirred for 1 hour, and filtered to obtain 4.5 g of compound (2-14).
  • Example 14-2 Compound (1-14) was obtained in the same manner as in Example 1-4, except that compound (2-14) obtained in Example 14-1 was used instead of compound (2-1).
  • Example 15 (Example 15-1) In a 50 mL round-bottomed flask, 0.6 g of phenyl chloroformate and 20 mL of N,N-dimethylformamide were placed, 1.0 g of the compound (7-1) obtained in Example 1-2 was added dropwise, and at 25° C. Stir for 12 hours. From NMR, it was confirmed that all the compound (7-1) was converted to the compound (7-15). After adding 10 mL of ion-exchanged water to the obtained solution, extraction operation was performed with 50 mL of dichloromethane. It was dehydrated with 5 g of magnesium sulfate and filtered to obtain 1.3 g of the compound (7-15).
  • Example 15-2 In a 100 mL pressure-resistant reactor, 15 g of compound (8-1) obtained according to the method described in Example 1-5 of Example of WO 2013/121984, dichloropentafluoropropane (AK, AK). -225) and 7.5 g of a 2.0 mol/L ammonia-methanol solution were added, and the mixture was stirred at 25° C. for 6 hours. The solvent was distilled off to obtain 14.8 g of compound (8-2).
  • Example 15-3 Compound (1-15) was obtained in the same manner as in Example 1-4, except that compound (2-15) obtained in Example 15-2 was used instead of compound (2-1).
  • Example 16 7.9 g of compound (1-16) was obtained in the same manner as in Example 15 except that 0.6 g of phenylchloroformate in Example 15-1 was changed to 0.7 g of phenylchlorothionoformate.
  • Example 17 Compound (8-4) was obtained according to the method described in Example 3-2 of WO2019/039341. The average value of x is 13. The molecular weight of R f is 4500. To a 50 mL eggplant-shaped flask, 10.0 g of the compound (8-4), 20 mL of 1,3-di(trifluoromethyl)benzene, and 1.0 g of the compound (7-1) obtained in Example 1-2 were added dropwise. , 0.50 g of triethylamine were added, and the mixture was stirred with heating under reflux overnight (12 hours). After adding methanol and stirring sufficiently, AC-6000 was added and stirred sufficiently. The AC-6000 layer was collected, the solvent was evaporated, and the residue was purified by silica gel column chromatography. 9.8 g of the compound (2-17) was obtained.
  • Example 17-2 Compound (1-17) was obtained in the same manner as in Example 1-4, except that compound (2-17) obtained in Example 17-1 was used instead of compound (2-1).
  • Example 18 In a 50 mL eggplant-shaped flask, 10.0 g of the compound (8-1) obtained in Example 1-3 and 2.1 g of ethyl acetate were placed, and after ice-cooling, 1.1 g of sodium methoxide was added. The temperature was gradually raised to 25° C. and the mixture was stirred for 12 hours. After adding 10 mL of water, 50 mL of AC-2000 was added for extraction operation. It was dehydrated with magnesium sulfate and then filtered to obtain 6.6 g of the compound (8-5).
  • Example 18-2 6.6 g of the compound (8-5) obtained in Example 18-1 was diluted with 30 mL of C 4 F 9 OC 2 H 5 (3M, Novec (registered trademark) 7200) and 1 mL of THF, and cooled with ice. After that, 5 mL of a THF solution of allyl magnesium chloride (1 mol/L) was added dropwise. The temperature was gradually raised to 25° C. and the mixture was stirred for 12 hours. Methanol was added to the obtained solution, and the mixture was sufficiently stirred, and then AC-6000 was added and sufficiently stirred. The AC-6000 layer was collected, the solvent was evaporated, and the residue was purified by silica gel chromatography. 2.7 g of the compound (2-18) was obtained.
  • Example 18-3 Compound (1-18) was obtained in the same manner as in Example 1-4, except that compound (2-18) obtained in Example 18-2 was used instead of compound (2-1).
  • Example 19 (Example 19-1) In a 50 mL round-bottomed flask, 5.0 g of the compound (2-18) obtained in Example 18-2 and 20 mL of AC-2000 were placed, and after cooling with ice, a lithium aluminum hydride solution in THF (2.5 mol/L ) was added dropwise. After gradually raising the temperature to 25° C., the mixture was stirred for 12 hours. The resulting solution was ice-cooled, 1 g of sodium sulfate decahydrate was added, and the mixture was stirred for 1 hour, then filtered to obtain 1.2 g of compound (2-19).
  • Example 19-2 Compound (1-19) was obtained in the same manner as in Example 1-4, except that compound (2-19) obtained in Example 19-1 was used instead of compound (2-1).
  • Example 20 (Example 20-1) A compound (2-20) was obtained in the same manner except that the compound (A) of Example 3 of Patent Document 3 was changed to the compound (2-19) obtained in Example 19-1 and methanesulfonyl chloride was changed to dimethylchlorophosphate. ) Got.
  • Example 20-2 Compound (1-20) was obtained in the same manner as in Example 1-4, except that compound (2-20) obtained in Example 20-1 was used instead of compound (2-1).
  • Example 21 (Example 21-1) A compound (2-21) was obtained in the same manner except that the compound (A) of Example 3 of Patent Document 3 was changed to the compound (2-19) obtained in Example 19-1.
  • Example 21-2 Compound (1-21) was obtained in the same manner as in Example 1-4, except that compound (2-21) obtained in Example 21-1 was used instead of compound (2-1).
  • Example 22 (Example 22-1) A compound (2-22) was obtained in the same manner except that the compound (A) of Example 1 of Patent Document 3 was changed to the compound (2-19) obtained in Example 19-1.
  • Example 22-2 Compound (1-22) was obtained in the same manner as in Example 1-4, except that compound (2-22) obtained in Example 22-1 was used instead of compound (2-1).
  • Example 23 A compound (10-1) was obtained in the same manner as in Example 11 of Patent Document 2.
  • Example 24 Compound (10-2) was obtained in the same manner as in Example 15 except that compound (4-1) was used instead of compound (7-1) in Example 15-1.
  • Example 25 Compound (10-3) was obtained in the same manner as in Example 24 except that phenylchloroformate in Example 15-1 was changed to phenylchlorothionoformate.
  • Example 26 Compound (10-4) was obtained in the same manner as in Example 17, except that compound (4-1) was used instead of compound (7-1) in Example 17-1.
  • Example 27 A compound (12-1) was obtained in the same manner as in Example 18-2 except that the compound (8-1) obtained in Example 1-3 was used instead of the compound (8-5) in Example 18-2. ..
  • Example 27-2 Compound (10-5) was obtained in the same manner as in Example 1-4, except that compound (12-1) obtained in Example 27-1 was used instead of compound (2-1).
  • Example 28 Compound (10-6) was obtained in the same manner as in Example 20, except that the compound (2-19) in Example 20-1 was changed to the compound (12-1) obtained in Example 27-1.
  • Example 29 A compound (10-7) was obtained in the same manner as in Example 21 except that the compound (2-19) in Example 21-1 was changed to the compound (12-1) obtained in Example 27-1.
  • Example 30 Compound (10-8) was obtained in the same manner as in Example 22 except that the compound (2-19) in Example 22-1 was changed to the compound (12-1) obtained in Example 27-1.
  • Example 31-2 In a 500 mL three-necked flask, 25.0 g (0.006 mm) of the compound (8-6) obtained in Example 31-1, 25.0 g of AE-3000, 7.2 g (0.06 mmol) of sodium fluoride and 20.0 g (0.06 mmol) of CF 3 CF 2 CF 2 OCF(CF 3 )COF was added, and the mixture was stirred at 50° C. for 12 hours. The obtained solution was filtered with a membrane filter and then concentrated to obtain 28.3 g of compound (8-7). The average value of x+y is 10. The molecular weight is 4600.
  • Example 31-3 250 mL of ClCF 2 CFClCF 2 OCF 2 CF 2 Cl (CFE-419) was put into a 500 mL nickel reactor, and nitrogen was bubbled. After the oxygen concentration was sufficiently lowered, 20% fluorine gas (diluted with nitrogen gas) was bubbled for 1 hour. The exhaust gas was neutralized with alkali. A CFE-419 solution of compound (8-7) (16% by mass, mass of compound (8-7): 25 g) was added over 2 hours. The ratio of the fluorine introduction rate (mol/hour) and the hydrogen atom introduction rate (mol/hour) in the compound (8-7) was controlled to be 2:1.
  • Example 31-4 Compound (2-31) was obtained in the same manner as in Example 1-3, except that compound (8-8) obtained in Example 31-3 was used instead of compound (8-1).
  • the molecular weight of Q f is 4000.
  • Example 31-5) Compound (1-31) was obtained in the same manner as in Example 1-4, except that compound (2-31) obtained in Example 31-4 was used instead of compound (2-1).
  • Examples 32-62 Manufacture and Evaluation of Articles A substrate was surface-treated with each of the compounds obtained in Examples 1 to 31 to obtain articles of Examples 32 to 62.
  • the surface treatment method the following dry coating method and wet coating method were used for each example.
  • a chemically strengthened glass was used as the base material.
  • the obtained articles were evaluated by the following methods. The results are shown in Tables 1 to 6.
  • the dry coating was performed using a vacuum vapor deposition device (VTR350M manufactured by ULVAC) (vacuum vapor deposition method).
  • VTR350M vacuum vapor deposition device manufactured by ULVAC
  • 0.5 g of each compound obtained in Examples 1 to 31 was filled in a molybdenum boat inside the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was evacuated to 1 ⁇ 10 ⁇ 3 Pa or less.
  • the boat on which the compound is placed is heated at a temperature rising rate of 10° C./min or less, and when the deposition rate by the crystal oscillation type film thickness meter exceeds 1 nm/sec, the shutter is opened to form a film on the surface of the base material. Started.
  • the shutter was closed to complete the film formation on the surface of the base material.
  • the substrate on which the compound was deposited was heat treated at 200° C. for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.
  • ⁇ Initial contact angle> For the surface layer, the initial contact angle of water or n-hexadecane was measured by the above measuring method. The evaluation criteria are as follows. Initial contact angle of water: A (excellent): 115 degrees or more. Good (Good): 110 degrees or more and less than 115 degrees. ⁇ (Fair): 100 degrees or more and less than 110 degrees. X (Not possible): less than 100 degrees. Initial contact angle of n-hexadecane: A (excellent): 66 degrees or more. Good (Good): 65 degrees or more and less than 66 degrees. ⁇ (OK): 63 degrees or more and less than 65 degrees. X (Not possible): less than 63 degrees.
  • ⁇ Light resistance> Light rays (650 W/m 2 , 300 to 700 nm) were applied to the surface layer at a black panel temperature of 63° C. using a desktop xenon arc lamp type accelerated light resistance tester (SUNTEST XLS+ manufactured by Toyo Seiki Co., Ltd.). After irradiation for 2,000 hours, the water contact angle was measured. The smaller the decrease in the water contact angle after the accelerated light resistance test, the smaller the decrease in performance due to light, and the better the light resistance.
  • the evaluation criteria are as follows. ⁇ (Excellent): Change in water contact angle after accelerated light resistance test is 2 degrees or less. Good (Good): Change in water contact angle after accelerated light resistance test is more than 2 degrees and 5 degrees or less. ⁇ (OK): Change in water contact angle after accelerated light resistance test was more than 5 degrees and 10 degrees or less. X (Not possible): Change in water contact angle after accelerated light resistance test exceeds 10 degrees.
  • ⁇ Abrasion resistance> Regarding the surface layer a reciprocating traverse tester (manufactured by KNT) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001), and a steel wool bonster (#0000) was used at a pressure of 98.07 kPa and a speed of 320 cm. After reciprocating 20,000 times/minute, the contact angle of water was measured. The smaller the decrease in the contact angle of water after rubbing, the smaller the decrease in performance due to rubbing, and the better the abrasion resistance. The evaluation criteria are as follows. ⁇ (Excellent): Change in water contact angle after reciprocating 20,000 times is 5 degrees or less.
  • Alkali resistance test The article was immersed in a 1N aqueous solution of sodium hydroxide (pH: 14) for 5 hours, washed with water and air-dried, and the water contact angle was measured by the above method. The smaller the decrease in the water contact angle after the test, the smaller the decrease in performance due to alkali, and the better the alkali resistance.
  • the evaluation criteria are as follows. ⁇ (excellent): Change in water contact angle after alkali resistance test is 2 degrees or less. ⁇ (Good): The change in water contact angle after the alkali resistance test is more than 2 degrees and 5 degrees or less. ⁇ (OK): The change in water contact angle after the alkali resistance test was more than 5 degrees and 10 degrees or less. X (Not possible): The change in water contact angle after the alkali resistance test exceeds 10 degrees.
  • Salt spray test A salt spray test was conducted according to JIS H8502. That is, the article was exposed to a salt water atmosphere in a salt spray tester (manufactured by Suga Test Instruments Co., Ltd.) for 300 hours, and then the water contact angle was measured by the above method. The smaller the decrease in the water contact angle after the test, the smaller the decrease in performance due to salt water, and the better the salt water resistance.
  • the evaluation criteria are as follows. ⁇ (excellent): The change in water contact angle after the salt spray test is 2 degrees or less. Good (Good): The change in water contact angle after the salt spray test was more than 2 degrees and 5 degrees or less. ⁇ (OK): Change in water contact angle after salt spray test was more than 5 degrees and 10 degrees or less. X (Not possible): The change in water contact angle after the salt spray test exceeds 10 degrees.
  • a fully-automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd., DMo-701 whose main surface was held horizontally was prepared. After placing the article on the surface (horizontal surface) of a polyethylene sheet (a hard polyethylene sheet (high-density polyethylene) manufactured by Hagitec Co., Ltd.) so that the surface layer is in contact, gradually tilt it using a fully automatic contact angle meter, The angle (sliding angle) formed by the surface layer of the article and the horizontal plane when the article started to slide was measured. The judgment criteria are shown below. The contact area between the article and the polyethylene sheet was 6 cm ⁇ 6 cm, and the load on the article was 0.98 N.
  • the value of haze was measured for each reciprocation of wiping, and the number of times of wiping at which haze was 10% or less from the initial value was measured. The less the number of times of wiping off, the easier it is to remove fingerprint stains, and the better the wiping performance of fingerprint stains.
  • the evaluation criteria are as follows. ⁇ (excellent): The number of times of wiping is 3 times or less. ⁇ (Good): The number of times of wiping is 4 to 5 times. ⁇ (OK): The number of times of wiping is 6 to 8 times. ⁇ (Not possible): The number of times of wiping is 9 or more.
  • Examples 32 to 53 and 62 using the compound (1) were excellent in initial water/oil repellency, light resistance, abrasion resistance, chemical resistance, slip resistance, and fingerprint stain removability.
  • the fluorine-containing compound of the present invention can be used in various applications in which lubricity and water/oil repellency are required.
  • display input device such as touch panel, surface protection coat of transparent glass or transparent plastic member, antifouling coat for kitchen, water repellent and antifouling coat for electronic devices, heat exchangers, batteries, etc., for toiletries
  • It can be used as an antifouling coat, a coat for a member requiring liquid repellency while conducting, a water repellent/waterproof/sliding coat for a heat exchanger, a low surface friction coat for a vibrating sieve or the inside of a cylinder, and the like.
  • More specific examples of use include a front protective plate for a display, an antireflection plate, a polarizing plate, an antiglare plate, or those whose surface is subjected to an antireflection film treatment, and a touch panel for devices such as mobile phones and personal digital assistants.
  • Various equipment such as seats and touch panel displays that have a display input device that operates on the screen with a person's finger or palm, decorative building materials around water such as toilets, baths, washrooms, kitchens, etc.
  • Surface protective coatings for machine parts, vacuum equipment parts, bearing parts, automobile parts, tools and the like can be mentioned.
  • the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2018-222872 filed on Nov. 28, 2018 are cited herein and incorporated as the disclosure of the specification of the present invention. Is.

Abstract

L'invention fournit un composé fluoré permettant de former une couche superficielle excellente en termes de propriétés d'élimination de traces d'empreinte digitale et de résistance au frottement, une composition comprenant un composé fluoré ainsi qu'un liquide de revêtement, et un article ainsi que son procédé de fabrication. Lequel article possède la couche superficielle excellente en termes de propriétés d'élimination de traces d'empreinte digitale et de résistance au frottement.　Plus précisément, l'invention concerne un composé fluoré qui possède un groupe organique fluoré monovalent ou divalent, un groupe silyle réactionnel dans lequel un groupe hydrolysable et/ou un groupe hydroxyle est lié à un groupe silicium, et un groupe de liaison liant le groupe organique fluoré monovalent et le groupe silyle réactionnel. Ce composé fluoré est caractéristique en ce que le groupe de liaison possède une région dans laquelle deux groupes polaires ou plus sont liés en série par l'intermédiaire d'un groupe organique divalent de 1 à 20 atomes de carbone, et les groupes polaires consistent en Ｃ（Ｏ）ＮＨ, ＮＨＣ（Ｏ）, ＮＨ, ＮＨＣ（Ｏ）ＮＨ, ＮＨＣ（Ｓ）ＮＨ, Ｓ（Ｏ）２ＮＨ, ＮＨＳ（Ｏ）２, Ｃ（Ｏ）, Ｃ（ＯＨ）, ou similaire.
PCT/JP2019/046024 2018-11-28 2019-11-25 Composé fluoré, composition comprenant un composé fluoré, liquide de revêtement, et article ainsi que procédé de fabrication de celui-ci WO2020111009A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020246301A1 (fr) * 2019-06-06 2020-12-10 信越化学工業株式会社 Polymère contenant un groupe fluoropolyéther et son procédé de production
WO2021100827A1 (fr) * 2019-11-22 2021-05-27 ダイキン工業株式会社 Composé silane contenant un groupe fluoropolyéther
WO2021182166A1 (fr) * 2020-03-09 2021-09-16 Ａｇｃ株式会社 Composé éther contenant du fluor et procédé de production associé, composé et procédé de production associé, composition d'éther contenant du fluor, liquide de revêtement, et article et procédés de production associés
WO2022163319A1 (fr) * 2021-01-28 2022-08-04 ダイキン工業株式会社 Composition contenant un composé silane contenant un groupe fluoropolyéther
WO2022209674A1 (fr) * 2021-03-30 2022-10-06 ダイキン工業株式会社 Composé de silane contenant un groupe fluoropolyéther

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WO2020246301A1 (fr) * 2019-06-06 2020-12-10 信越化学工業株式会社 Polymère contenant un groupe fluoropolyéther et son procédé de production
WO2021100827A1 (fr) * 2019-11-22 2021-05-27 ダイキン工業株式会社 Composé silane contenant un groupe fluoropolyéther
JP2021088551A (ja) * 2019-11-22 2021-06-10 ダイキン工業株式会社 フルオロポリエーテル基シラン含有化合物
JP7319242B2 (ja) 2019-11-22 2023-08-01 ダイキン工業株式会社 フルオロポリエーテル基シラン含有化合物
WO2021182166A1 (fr) * 2020-03-09 2021-09-16 Ａｇｃ株式会社 Composé éther contenant du fluor et procédé de production associé, composé et procédé de production associé, composition d'éther contenant du fluor, liquide de revêtement, et article et procédés de production associés
WO2022163319A1 (fr) * 2021-01-28 2022-08-04 ダイキン工業株式会社 Composition contenant un composé silane contenant un groupe fluoropolyéther
JP2022115807A (ja) * 2021-01-28 2022-08-09 ダイキン工業株式会社 フルオロポリエーテル基含有シラン化合物を含有する組成物
WO2022209674A1 (fr) * 2021-03-30 2022-10-06 ダイキン工業株式会社 Composé de silane contenant un groupe fluoropolyéther
JP2022155508A (ja) * 2021-03-30 2022-10-13 ダイキン工業株式会社 フルオロポリエーテル基含有シラン化合物
JP7152696B1 (ja) 2021-03-30 2022-10-13 ダイキン工業株式会社 フルオロポリエーテル基含有シラン化合物

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