WO2017104249A1 - Silane modifié par un polymère contenant un groupe fluoropolyéther, agent de traitement de surface et objet - Google Patents

Silane modifié par un polymère contenant un groupe fluoropolyéther, agent de traitement de surface et objet Download PDF

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WO2017104249A1
WO2017104249A1 PCT/JP2016/080683 JP2016080683W WO2017104249A1 WO 2017104249 A1 WO2017104249 A1 WO 2017104249A1 JP 2016080683 W JP2016080683 W JP 2016080683W WO 2017104249 A1 WO2017104249 A1 WO 2017104249A1
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group
containing polymer
formula
carbon atoms
integer
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PCT/JP2016/080683
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隆介 酒匂
高至 松田
祐治 山根
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信越化学工業株式会社
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Priority to KR1020187019089A priority Critical patent/KR102648009B1/ko
Priority to CN201680071632.4A priority patent/CN108368253B/zh
Priority to JP2017556388A priority patent/JP6642589B2/ja
Publication of WO2017104249A1 publication Critical patent/WO2017104249A1/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
    • 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
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • 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
    • 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 fluoropolyether group-containing polymer-modified silane, and more specifically, a fluoropolyether group-containing polymer-modified silane that forms a film having excellent slipperiness, a surface treatment agent containing the silane, and the surface treatment agent.
  • the article is surface-treated with (i.e., having a cured coating of the surface treatment agent on the surface).
  • a fluoropolyether group-containing compound has water and oil repellency, chemical resistance, lubricity, releasability, antifouling property and the like because its surface free energy is very small. Utilizing its properties, it is widely used industrially for water and oil repellent and antifouling agents such as paper and fiber, lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, and protective films. ing. However, the property means that it is non-adhesive and non-adhesive to other substrates at the same time, and even if it can be applied to the surface of the substrate, it was difficult to make the film adhere to it. .
  • a silane coupling agent is well known as a material for bonding a substrate surface such as glass or cloth and an organic compound, and is widely used as a coating agent for various substrate surfaces.
  • the silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule.
  • the hydrolyzable silyl group causes a self-condensation reaction with moisture in the air to form a film.
  • the coating becomes a strong coating having durability by chemically and physically bonding the hydrolyzable silyl group to the surface of glass or metal.
  • Lenses and antireflection films surface-treated with a composition containing a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced into the fluoropolyether group-containing compound are excellent in wear resistance and releasability. The slipperiness is not enough.
  • Rf is a monovalent fluorooxyalkyl group or divalent fluorooxyalkylene group-containing polymer residue
  • Y is a divalent to hexavalent hydrocarbon group optionally having a siloxane bond and a silylene group.
  • R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group
  • X is independently a hydrolyzable group
  • n is an integer of 1 to 3
  • m is an integer of 1 to 5.
  • Patent Document 6 JP-A-2015-199906
  • the fluoropolyether group-containing polymer-modified silane and / or a partial hydrolysis-condensation product thereof is proposed.
  • the coating film formed from the surface treating agent contained exhibits high water / oil repellency and abrasion resistance. However, the slipperiness has not been improved.
  • the present invention has been made in view of the above circumstances, a fluoropolyether group-containing polymer-modified silane capable of forming a water- and oil-repellent layer excellent in slipperiness, a surface treatment agent containing the silane, and the surface treatment It is an object to provide an article surface-treated with an agent (that is, having a cured film of the surface treatment agent on the surface).
  • the present inventors have determined that the hydroxyl group represented by the following general formula (1) in the fluoropolyether group-containing polymer-modified silane is represented by the following -QR 'group:
  • the present inventors have found that a protected fluoropolyether group-containing polymer-modified silane can form a water / oil repellent layer excellent in slipperiness and weather resistance and excellent in storage stability, and has led to the present invention.
  • the present invention provides the following fluoropolyether group-containing polymer-modified silane, surface treatment agent and article.
  • Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue
  • Y is a divalent to hexavalent hydrocarbon group which may have a siloxane bond and / or a silylene group
  • R I is an alkyl group having 1 to 4 carbon atoms or a phenyl group
  • X is a hydroxyl group or a hydrolyzable group
  • Q is a divalent organic group which may have a siloxane bond and / or a silylene group
  • R 'Is a monovalent fluoroalkyl group, a monovalent fluorooxyalkylene group-containing polymer residue, an alkyl group having 1 to 4 carbon atoms, or a phenyl group
  • n is an integer of 1 to 3
  • m is 1 to 5
  • ⁇ is 1
  • Y represents an alkylene group having 3 to 10 carbon atoms, an alkylene group having 8 to 16 carbon atoms including a phenylene group, and an alkylene group having 2 to 10 carbon atoms has a silalkylene structure or a silarylene structure.
  • the fluoropolyether group-containing polymer-modified silane according to any one of [1] to [3], which is one kind of group.
  • each X independently represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or 2 to 10 carbon atoms.
  • Q is a divalent organic group represented by the following formula (4): Silane.
  • R ′′ is a C 1-10 alkylene group which may have any of ketone, ester, amide, ether, sulfide, amine and phenylene, or carbonyl group
  • W is a silicon atom
  • the surface treatment agent containing a fluoropolyether group-containing polymer-modified silane in which a hydroxyl group bonded to a carbon atom of the present invention is sealed with the above-mentioned -QR 'group forms a water- and oil-repellent layer excellent in slipperiness. Can do.
  • the fluoropolyether group-containing polymer-modified silane of the present invention is represented by the following general formula (1).
  • Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue
  • Y is a divalent to hexavalent hydrocarbon group which may have a siloxane bond and / or a silylene group
  • R I is an alkyl group having 1 to 4 carbon atoms or a phenyl group
  • X is a hydroxyl group or a hydrolyzable group
  • Q is a divalent organic group which may have a siloxane bond and / or a silylene group
  • R 'Is a monovalent fluoroalkyl group, a monovalent fluorooxyalkylene group-containing polymer residue, an alkyl group having 1 to 4 carbon atoms, or a phenyl group
  • n is an integer of 1 to 3
  • m is 1 to 5
  • ⁇ is 1 or 2.
  • the fluoropolyether group-containing polymer-modified silane of the present invention comprises a monovalent or divalent fluorooxyalkylene group-containing polymer residue (Rf), a hydrolyzable silyl group such as an alkoxysilyl group, or a hydroxyl group-containing silyl group (—Si (R) 3-n (X) n ) is a structure in which a siloxane bond and / or a divalent to hexavalent hydrocarbon chain (Y) optionally having a silylene group is bonded via a carbon atom, Further, a divalent organic group (Q) which may have a siloxane bond and / or a silylene group as a linking group to a hydroxyl group bonded to a carbon atom in the polymer as an intermediate, preferably a ketone, ester, amide, C 1-10 alkylene group or carbonyl group (R ′′) which may have ether, sulfide, amine,
  • Rf is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2) (hereinafter sometimes referred to as a fluorooxyalkyl group) Is preferred.
  • a fluorooxyalkyl group a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2) (hereinafter sometimes referred to as a fluorooxyalkyl group) Is preferred.
  • p, q, r and s are each an integer of 0 to 200
  • p + q + r + s an integer of 3 to 200
  • t is an integer of 1 to 3
  • each repeating unit is linear or branched. And each repeating unit may be bonded at random.
  • T is an integer of 1 to 3, preferably 1 or 2, and C t F 2t may be linear or branched.
  • Rf divalent fluorooxyalkylene group-containing polymer residue
  • p ′, q ′, r ′ and s ′ are each an integer of 1 or more, and the upper limit thereof is the same as the upper limit of p, q, r and s.
  • U is an integer of 1 to 24
  • Each repeating unit may be bonded at random.
  • Y may have a siloxane bond ((di) organosiloxane unit etc.) and / or a silylene group (diorganosilylene group), preferably 2 to 4, more preferably 2 to 4.
  • a divalent hydrocarbon group is preferable, and a coating film having excellent weather resistance and abrasion resistance can be provided by not including a linking group having low binding energy (such as an ether bond) in the molecule.
  • Y examples include a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), a C3-C10 alkylene group such as a hexamethylene group, and a carbon such as a phenylene group.
  • An alkylene group containing an arylene group having 6 to 8 carbon atoms for example, an alkylene / arylene group having 8 to 16 carbon atoms
  • an alkylene group having 2 to 10 carbon atoms having a silalkylene structure both ends of the alkylene group are diorganosilylene
  • a divalent group bonded via a group or a silarylene structure (a structure in which both ends of the arylene group are blocked with a diorganosilylene group)
  • 2 to 10 silicon atoms preferably A divalent to hexavalent group, preferably a divalent to tetravalent group having an alkylene group bonded to the bond of 2 to 5 linear organopolysiloxane residues, Divalent to hexavalent, preferably divalent to tetravalent, etc.
  • an alkylene group having 3 to 10 carbon atoms, an alkylene group having 8 to 16 carbon atoms including a phenylene group, and an alkylene group having 2 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure.
  • An alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms.
  • a tetravalent group or 2 to 2 having an alkylene group having 2 to 10 carbon atoms bonded to a bond of a branched or cyclic organopolysiloxane residue having 3 to 10, preferably 3 to 5 silicon atoms.
  • tetravalent groups Ri more preferably an alkylene group having 3 to 6 carbon atoms.
  • examples of the silalkylene structure and the silarylene structure include those shown below.
  • R 1 represents a methyl group, an ethyl group, a propyl group, an alkyl group having 1 to 4 carbon atoms such as butyl group, an aryl group having 6 to 10 carbon atoms such as a phenyl group
  • R 1 is also the same
  • R 2 is an alkylene group having 1 to 4 carbon atoms such as a methylene group, ethylene group, propylene group (trimethylene group or methylethylene group), or an arylene group having 6 to 10 carbon atoms such as a phenylene group. is there.
  • Examples of the hexavalent organopolysiloxane residue include those shown below.
  • R 1 is the same as above, g is an integer of 1 to 9, preferably 1 to 4, h is an integer of 2 to 6, preferably 2 to 4, and j is 0) An integer of ⁇ 8, preferably 0 or 1, h + j is an integer of 3 to 10, preferably an integer of 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3.)
  • Y include the following groups.
  • X is a hydroxyl group or a hydrolyzable group which may be different from each other.
  • examples of such X include hydroxyl groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups and the like, alkoxy groups having 1 to 10 carbon atoms, methoxymethoxy groups, methoxyethoxy groups and the like having 2 to 10 carbon atoms.
  • Examples include an alkoxy-substituted alkoxy group, an acyloxy group having 2 to 10 carbon atoms such as an acetoxy group, an alkenyloxy group having 2 to 10 carbon atoms such as an isopropenoxy group, a halogen atom such as a chloro atom, a bromo atom, and an iodo atom.
  • a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro atom are preferable.
  • R is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, and a methyl group is particularly preferable.
  • n is an integer of 1 to 3, preferably 2 or 3, and 3 is more preferable from the viewpoint of reactivity and adhesion to a substrate.
  • m is an integer of 1 to 5, and if it is less than 1, the adhesion to the substrate is lowered, and if it is 6 or more, the terminal alkoxy value is too high to adversely affect the performance. Yes, 1 is particularly preferable.
  • Q is a divalent organic group which may have a siloxane bond and / or a silylene group, and is particularly preferably a divalent organic group represented by the following formula (4).
  • R ′′ is a C 1-10 alkylene group which may have any of ketone, ester, amide, ether, sulfide, amine and phenylene, or carbonyl group
  • W is a silicon atom
  • R ′′ is specifically carbon such as methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group, hexamethylene group).
  • An alkylene group having 1 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms are bonded to each other via an arylene group such as a ketone, ester, amide, ether, sulfide, amine, or a phenylene group having 6 to 8 carbon atoms.
  • a carbonyl group preferably an alkylene group having 1 to 4 carbon atoms, a divalent group in which alkylene groups having 1 to 4 carbon atoms are bonded to each other via an ether, and a carbonyl group.
  • R ′′ include, for example, the following groups.
  • R 1 represents a methyl group, an ethyl group, a propyl group, an alkyl group having 1 to 4 carbon atoms such as butyl group, an aryl group having 6 to 10 carbon atoms such as a phenyl group
  • R 1 is also the same
  • R 2 is an alkylene group having 1 to 4 carbon atoms such as a methylene group, ethylene group, propylene group (trimethylene group or methylethylene group), or an arylene group having 6 to 10 carbon atoms such as a phenylene group. is there.
  • Examples of the linear divalent organopolysiloxane residue having 2 to 40, preferably 3 to 10, silicon atoms include the following. (In the formula, R 1 is the same as above. F is an integer of 1 to 39, preferably an integer of 2 to 9.)
  • R ′ is a monovalent fluoroalkyl group (for example, a fluoroalkyl group having 1 to 6 carbon atoms), a monovalent fluorooxyalkylene group-containing polymer residue, or a methyl group having 1 to 4 carbon atoms.
  • An alkylene group-containing polymer residue is preferred.
  • R ′ when R ′ is a monovalent fluorooxyalkylene group-containing polymer residue, the R ′ is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2).
  • Examples of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) include those represented by the following formula.
  • the number of repeating units (or the degree of polymerization) constituting the fluorooxyalkyl group or fluorooxyalkylene group can take any number satisfying the above formulas (2) and (3). It is.
  • p1 is an integer of 5 to 100
  • q1 is an integer of 5 to 100
  • p1 + q1 is an integer of 10 to 105.
  • Examples of the method for preparing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and ⁇ being 1 include the following methods.
  • a fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain that is, a polymer having a monovalent fluorooxyalkylene group-containing polymer residue and two olefin moieties at one end of the molecular chain
  • a solvent for example
  • An organosilicon compound having a SiH group and a hydrolyzable terminal group in a molecule such as trimethoxysilane is dissolved in a fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene, and a hydrosilylation reaction catalyst such as chloride
  • a platinic acid / vinylsiloxane complex in a toluene solution at a temperature of 40 to 120 ° C., preferably 60 to 100 ° C.,
  • a fluorooxyalkyl group-containing polymer having two olefin moieties at one end of a molecular chain is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene, and SiH is contained in a molecule such as trichlorosilane.
  • a fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene
  • An organosilicon compound having a group and a hydrolyzable end group for example, a halogen atom bonded with a silicon atom such as a chlorine atom
  • a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex.
  • hydrosilylation addition reaction and aging at a temperature of 1 ° C., preferably 60 to 100 ° C., more preferably about 80 ° C. for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours.
  • Hydrolyzable substituents on silyl groups (halogen atoms, etc.) such as alkoxy groups such as methoxy groups To convert to.
  • organosilicon compound having a SiH group and a hydrolyzable end group in the molecule instead of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, a SiH group-containing organosilicon compound having no hydrolyzable end group can also be used. As an organosilicon compound having no hydrolyzable end groups in the molecule and having two or more SiH groups.
  • a fluorooxyalkyl group-containing polymer having two olefin sites at one end of the molecular chain and an organosilicon having two or more SiH groups without hydrolyzable end groups in the molecule Hydrosilylation addition reaction of the compound with equimolar or more to produce a reaction product (intermediate) having two residual SiH groups at one end of the molecular chain, and then SiH at the polymer end of the reaction product (intermediate) Group and an organosilicon compound having an olefin moiety and a hydrolyzable end group in a molecule such as allyltrimethoxysilane in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex,
  • the temperature is 60 to 100 ° C., more preferably about 80 ° C. for 1 to 72 hours, preferably 20 to 36 hours, more preferably
  • a fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain a fluorooxyalkyl group-containing polymer represented by the following general formula (5) can be exemplified.
  • Rf, Q, and R ′ are the same as above.
  • Z is a divalent hydrocarbon group.
  • Z is a divalent hydrocarbon group, preferably a divalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, specifically, a methylene group, an ethylene group, C1-C8 alkylene group such as propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group, etc., and C6-C8 such as phenylene group And an alkylene group containing an arylene group (for example, an alkylene / arylene group having 7 to 8 carbon atoms). Z is preferably a linear alkylene group having 1 to 4 carbon atoms.
  • Preferred examples of the fluorooxyalkyl group-containing polymer represented by the formula (5) include those shown below.
  • the number of repeats (or the degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group can be any number satisfying the formula (2) in Rf. (Wherein r1 is an integer of 1 to 100, and p1, q1, and p1 + q1 are the same as above.)
  • a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of a molecular chain and two olefin sites that is, a monovalent polymer
  • a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of a molecular chain and two olefin sites that is, A monovalent fluorooxyalkylene group-containing polymer residue, a polymer having two olefin moieties and a hydroxyl group at one end of the molecular chain, and a fluorooxyalkyl group-containing polymer having an acid fluoride at the terminal end of the molecular chain.
  • desolvation is performed using a solvent at a temperature of 0 to 100 ° C., preferably 25 to 80 ° C., more preferably 60 ° C. for 1 to 48 hours, preferably 5 to 36 hours, more preferably about 20 hours.
  • a hydrogen halide (dehydrofluorination) reaction or the like is performed.
  • the fluorooxyalkyl group-containing polymer having an acid fluoride at one end of the molecular chain is a group having at one end of the molecular chain, in addition to the above-mentioned acid fluoride, other acid halides (for example, acid chloride), acid anhydrides Products, esters (for example, alkyl esters such as methyl esters), carboxylic acids, and the like can also be used.
  • acid halides for example, acid chloride
  • esters for example, alkyl esters such as methyl esters
  • carboxylic acids and the like
  • Specific examples of the perfluorooxyalkyl group-containing polymer having these groups (acid halide, acid anhydride, ester, carboxylic acid, etc.) at one end of the molecular chain include those shown below. (Wherein p1, q1, and p1 + q1 are the same as above)
  • the addition amount of the fluorooxyalkyl group-containing polymer having a functional group such as acid fluoride at the molecular chain end is based on 1 equivalent of the reactive end group (hydroxyl) of the fluorooxyalkyl group-containing polymer having a hydroxyl group at the molecular chain end. 0.5 to 1 equivalent, more preferably 0.8 to 1 equivalent, and still more preferably about 0.9 equivalent.
  • amines and alkali metal bases can be used.
  • amines and alkali metal bases include diisopropylethylamine, pyridine, DBU, and imidazole.
  • alkali metal bases sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, t-butoxypotassium, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis And (trimethylsilyl) amide.
  • the amount of the base used is 1 to 10 equivalents, more preferably 1 to 3 equivalents, and even more preferably about 2 equivalents to 1 equivalent of the reactive terminal group of the polymer having a hydroxyl group at one end of the molecular chain. Can be used.
  • the solvent used is preferably a fluorinated solvent
  • the fluorinated solvent is 1,3-bis (trifluoromethyl) benzene, trifluoro Methylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3- Hydrofluoroether (HFE) solvents such as methoxy-2- (trifluoromethyl) pentane (3M, trade name: Novec series), perfluoro solvents (3M) consisting of fully fluorinated compounds Manufactured, product name: Florinert series).
  • HFE Hydrofluoroether
  • the amount of the solvent used is 10 to 300 parts by weight, preferably 50 to 150 parts by weight, more preferably about 100 parts by weight with respect to 100 parts by weight of the fluorooxyalkylene group-containing polymer having two olefin moieties at one end of the molecular chain. Can be used.
  • fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of a molecular chain as a raw material used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5) and having two olefin moieties Include the following. (In the formula, r1, p1, q1, and p1 + q1 are the same as above.)
  • an acid fluoride group (—C ( ⁇ O) —F at the terminal of the molecular chain is used.
  • the perfluorooxyalkyl group-containing polymer as a raw material used for the preparation of the fluorooxyalkyl group-containing polymer having a hydroxyl group at the terminal end of the molecular chain and having two olefin moieties is a group having at the terminal end of the molecular chain
  • acid fluorides described above other acid halides (such as acid chlorides), acid anhydrides, esters, carboxylic acids, amides, and the like can also be used.
  • Specific examples of the perfluorooxyalkyl group-containing polymer having these groups at one end of the molecular chain include those shown below. (Wherein p1, q1, and p1 + q1 are the same as above)
  • nucleophilic agent used for the preparation of a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin moieties examples include allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5-hexenylmagnesium halide and the like can be used. It is also possible to use a corresponding lithium reagent.
  • the amount of the nucleophilic agent used is 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and even more preferably about 3 equivalents with respect to 1 equivalent of the reactive end group of the perfluorooxyalkyl group-containing polymer. Can be used.
  • Examples of the solvent used for the preparation of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin moieties include 1,3-bis (trifluoromethyl) benzene, Trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro- Hydrofluoroether (HFE) solvents such as 3-methoxy-2- (trifluoromethyl) pentane (trade name: Novec series, manufactured by 3M), perfluoro solvents composed of fully fluorinated compounds ( 3M, product name: Florinart series) And the like.
  • HFE Hydrofluoroether
  • ether solvents such as tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used as the organic solvent.
  • the solvent may be used in an amount of 10 to 300 parts by weight, preferably 100 to 200 parts by weight, and more preferably about 150 parts by weight with respect to 100 parts by weight of the perfluorooxyalkyl group-containing polymer.
  • the reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by a liquid separation operation.
  • the obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain.
  • the hydrosilane used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5) includes a polydimethylsiloxane-terminated hydrosilane having 2 to 40 silicon atoms in which one of the end groups is sealed with an alkyl group, a terminal Examples thereof include polydimethylsiloxane-terminated hydrosilanes having 2 to 40 silicon atoms in which one of the groups is sealed with a fluoroalkyl group or a fluorooxyalkyl group.
  • Specific examples of the hydrosilane used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5) include those shown below. (Wherein p1, q1, and p1 + q1 are the same as above)
  • the amount of the hydrosilane used is 1 to 5 equivalents, more preferably 1 to 2 with respect to 1 equivalent of the reactive end group of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one molecular chain terminal and having two olefin moieties.
  • An equivalent amount, more preferably about 1.2 equivalents can be used.
  • a platinum group metal catalyst such as rhodium, palladium, ruthenium or a boron catalyst
  • platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium
  • boron catalysts such as tris (pentafluorophenyl) borane, and the like can be given.
  • the dehydrogenation catalyst is used in an amount of 0.01 to 0.0005 equivalents relative to 1 equivalent of a reactive end group of a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin moieties.
  • the amount is preferably 0.007 to 0.001 equivalent, more preferably about 0.005 equivalent.
  • Examples of the solvent used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5) include fluorine-containing aromatics such as 1,3-bis (trifluoromethyl) benzene and trifluoromethylbenzene as fluorine-based solvents.
  • Hydrocarbon solvents methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro- Hydrofluoroether (HFE) solvents such as 3-methoxy-2- (trifluoromethyl) pentane (trade name: Novec series, manufactured by 3M), perfluoro solvents composed of fully fluorinated compounds ( 3M, trade name: Florinart series).
  • HFE Hydrofluoroether
  • ether solvents such as tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used as the organic solvent.
  • the amount of the solvent used is 10 to 300 parts by weight, preferably 50 to 150 parts by weight, more preferably 100 parts by weight of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin moieties. About 100 parts by mass can be used.
  • the solvent used is preferably a fluorinated solvent
  • the fluorinated solvent is 1,3-bis ( Trifluoromethyl) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5 , 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane and other hydrofluoroether (HFE) solvents (trade name: Novec series, manufactured by 3M), composed of fully fluorinated compounds Perfluoro solvent (made by 3M, trade name: Florinato Siri ), And the like.
  • HFE hydrofluoroether
  • the amount of the solvent used is 10 to 300 parts by weight, preferably 50 to 150 parts by weight, more preferably about 100 parts by weight with respect to 100 parts by weight of the fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain. Can be used.
  • an organosilicon compound having a SiH group and a hydrolyzable end group in the molecule includes the following general formula: Compounds represented by (6) to (9) are preferred. Wherein R, X, n, R 1 , R 2 , g and j are the same as above. R 3 is a divalent hydrocarbon group having 2 to 8 carbon atoms. I is an integer of 2 to 9 (It is preferably an integer of 2 to 4, and i + j is an integer of 2 to 9.)
  • the divalent hydrocarbon group having 2 to 8 carbon atoms, preferably 2 to 3 carbon atoms of R 3 includes methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, Methylpropylene groups), alkylene groups such as hexamethylene groups and octamethylene groups, arylene groups such as phenylene groups, or combinations of two or more of these groups (alkylene / arylene groups, etc.).
  • ethylene Group and trimethylene group are preferred.
  • organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule examples include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, and triisopropenoxysilane. , Triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following organosilicon compounds.
  • a fluorooxyalkyl group-containing polymer having two olefin sites at one end of the molecular chain and a SiH group in the molecule The amount of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule when reacting with the organosilicon compound having a hydrolyzable end group is the fluorooxy having two olefin moieties at one end of the molecular chain. It can be used in an amount of 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, and even more preferably about 3 equivalents with respect to 1 equivalent of reactive end group of the alkyl group-containing polymer.
  • organosilicon having no hydrolyzable end group in the molecule and having two or more SiH groups As the compound, compounds represented by the following general formulas (10) to (12) are preferable. (In the formula, R 1 , R 2 , g, j and i are the same as above.)
  • organosilicon compound having no hydrolyzable end group in the molecule and having two or more SiH groups examples include the following.
  • a fluoropolyether group-containing polymer-modified silane represented by the formula (1) where ⁇ is 1, a fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain and hydrolyzability in the molecule The amount of the organosilicon compound having no hydrolyzable end group in the molecule and having two or more SiH groups in the molecule when reacting with the organosilicon compound having two or more SiH groups does not have an end group.
  • an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule includes the following general formula:
  • the compound represented by (13) is preferred.
  • R, X, and n are the same as above.
  • V is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms.
  • V is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms.
  • the divalent hydrocarbon group having 1 to 6 carbon atoms include a methylene group and an ethylene group.
  • a propylene group trimethylene group, methylethylene group
  • a butylene group tetramethylene group, methylpropylene group
  • an alkylene group such as a hexamethylene group
  • a phenylene group is preferably a single bond or a methylene group.
  • ⁇ 1, a fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain and hydrolyzability in the molecule Olefin moiety in the molecule when reacting a reaction product of an organosilicon compound having two or more SiH groups with no end group and an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule
  • the amount of the organosilicon compound having hydrolyzable end groups is such that the fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain and no hydrolyzable end groups in the molecule, SiH groups 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, more preferably 1 equivalent of the reactive terminal group of the reaction product with the organosilicon compound having two or more.
  • Can be used is about 3 equivalent
  • hydrosilylation reaction catalysts include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum chloride
  • examples include complexes of acids with olefins, aldehydes, vinyl siloxanes, acetylene alcohols, and the like, and platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium.
  • platinum compounds such as vinylsiloxane coordination compounds.
  • the amount of the hydrosilylation reaction catalyst used is a fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain, or this polymer and the molecule having no hydrolyzable end groups and at least two SiH groups. It is used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal (mass), based on the amount of the reactant with the organosilicon compound.
  • the target compound can be obtained by depressurizingly distilling a solvent and an unreacted substance.
  • a compound represented by the following formula as a fluorooxyalkyl group-containing polymer having two olefin moieties at one end of a molecular chain
  • trimethoxysilane is used as the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, a compound represented by the following formula is obtained.
  • Examples of the preparation method of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and ⁇ being 2 include the following methods.
  • Fluoroalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain ie, a polymer residue having a divalent fluorooxyalkylene group and two olefin moieties at both ends of the molecular chain
  • a solvent such as a fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene
  • an organosilicon compound having a SiH group and a hydrolyzable end group in a molecule such as trimethoxysilane is hydrosilylated.
  • a reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex
  • organosilicon compound having a SiH group and a hydrolyzable end group in the molecule instead of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, a SiH group-containing organosilicon compound having no hydrolyzable end group can be used. As an organosilicon compound having no hydrolyzable end groups in the molecule and having two or more SiH groups.
  • a fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain and an organic compound having no hydrolyzable end groups in the molecule and having two or more SiH groups After reacting the silicon compound with equimolar or more to produce a reaction product (intermediate) having two residual SiH groups at both ends of the molecular chain, the SiH group at the polymer end of the reaction product (intermediate) And an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule, such as allyltrimethoxysilane, in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, preferably 40 to 120 ° C. Is aged at a temperature of 60 to 100 ° C., more preferably about 80 ° C. for 1 to 72 hours, preferably 20
  • fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain a fluorooxyalkylene group-containing polymer represented by the following general formula (14) can be exemplified.
  • Rf, Z, Q, and R ′ are the same as above.
  • Preferred examples of the fluorooxyalkylene group-containing polymer represented by the formula (14) include those shown below.
  • the number of repeating units (or the degree of polymerization) constituting the fluorooxyalkylene group can be any number satisfying the formula (3) in Rf. (Wherein p1, q1, and p1 + q1 are the same as above)
  • Examples of the method for preparing the fluorooxyalkylene group-containing polymer represented by the formula (14) include a fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain and two olefin moieties at both ends of the molecular chain.
  • a divalent fluorooxyalkylene group-containing polymer residue a polymer having two olefinic sites at both ends of the molecular chain and a hydroxyl group
  • hydrosilane in the presence of a dehydrogenation catalyst, 0
  • the dehydrogenation reaction is carried out at a temperature of -60 ° C, preferably 15-35 ° C, more preferably about 25 ° C for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour.
  • Another method for preparing the fluorooxyalkylene group-containing polymer represented by the above formula (14) is a fluorooxyalkylene having a hydroxyl group at both ends of the molecular chain and two olefin moieties at both ends of the molecular chain.
  • a group-containing polymer that is, a polymer having a divalent fluorooxyalkylene group-containing polymer residue, two olefin moieties at each of both ends of the molecular chain and a hydroxyl group
  • an acid fluoride at one end of the molecular chain
  • the fluorooxyalkyl group-containing polymer having an acid fluoride at one end of the molecular chain includes, in addition to the acid fluoride described above, an acid halide, an acid anhydride, an ester, a carboxylic acid, etc. Can be used.
  • Specific examples of the perfluorooxyalkyl group-containing polymer having these groups (acid halide, acid anhydride, ester, carboxylic acid, etc.) at one end of the molecular chain include those shown below. (Wherein p1, q1, and p1 + q1 are the same as above)
  • the addition amount of the fluorooxyalkyl group-containing polymer having an acid fluoride at one end of the molecular chain is 0. 1 equivalent to 1 equivalent of the reactive end group (hydroxyl group) of the fluorooxyalkylene group-containing polymer having a hydroxyl group at both ends of the molecular chain. 5 to 1 equivalent, more preferably 0.8 to 1 equivalent, and still more preferably about 0.9 equivalent can be used.
  • amines and alkali metal bases can be used.
  • amines and alkali metal bases include diisopropylethylamine, pyridine, DBU, and imidazole.
  • alkali metal bases sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, t-butoxypotassium, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis And (trimethylsilyl) amide.
  • the amount of the base used is 1 to 10 equivalents, more preferably 1 to 3 equivalents, and still more preferably about 2 equivalents to 1 equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain. Can be used.
  • the solvent used is preferably a fluorinated solvent, and the fluorinated solvent is 1,3-bis (trifluoromethyl) benzene, trifluoro Methylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3- Hydrofluoroether (HFE) solvents such as methoxy-2- (trifluoromethyl) pentane (3M, trade name: Novec series), perfluoro solvents (3M) consisting of fully fluorinated compounds Product name: Florinert series) .
  • HFE Hydrofluoroether
  • the solvent is used in an amount of 10 to 300 parts by weight, preferably 50 to 150 parts by weight, and more preferably about 100 parts by weight with respect to 100 parts by weight of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain. Can do.
  • fluorooxyalkylene group-containing polymer having a hydroxyl group at both ends of a molecular chain and two olefin moieties at both ends of the molecular chain used for the preparation of a fluorooxyalkylene group-containing polymer represented by formula (14)
  • Specific examples include those shown below. (Wherein p1, q1, and p1 + q1 are the same as above)
  • a hydroxyl group is introduced together with the olefin moiety.
  • an acid halide, an acid anhydride, an ester, a carboxylic acid, an amide, or the like can be used in addition to the above-described acid fluoride as groups having both ends of the molecular chain.
  • Specific examples of the perfluorooxyalkylene group-containing polymer having these groups at both ends of the molecular chain include those shown below. (Wherein p1, q1, and p1 + q1 are the same as above)
  • nucleophile used for the preparation of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain examples include allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5-hexenyl magnesium halide and the like. Can be used. It is also possible to use a corresponding lithium reagent.
  • the amount of the nucleophilic agent used can be 4 to 10 equivalents, more preferably 5 to 7 equivalents, and even more preferably about 6 equivalents with respect to 1 equivalent of the reactive end group of the perfluorooxyalkylene group-containing polymer. .
  • a solvent used for the preparation of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain 1,3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, methyl nona Fluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2- ( Hydrofluoroether (HFE) solvents such as trifluoromethyl) pentane (trade name: Novec series, manufactured by 3M), perfluoro solvents (trade name: manufactured by 3M, trade name) composed of fully fluorinated compounds Fluorinert series).
  • HFE Hydrofluoroether
  • ether solvents such as tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used as the organic solvent.
  • the solvent may be used in an amount of 10 to 300 parts by weight, preferably 100 to 200 parts by weight, and more preferably about 150 parts by weight with respect to 100 parts by weight of the perfluorooxyalkylene group-containing polymer.
  • reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by a liquid separation operation.
  • the obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain.
  • the hydrosilane used for the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (14) includes a polydimethylsiloxane-terminated hydrosilane having 2 to 40 silicon atoms, one of the end groups sealed with an alkyl group, Examples thereof include polydimethylsiloxane-terminated hydrosilanes having 2 to 40 silicon atoms in which one of the groups is sealed with a fluoroalkyl group or a fluorooxyalkyl group.
  • the amount of hydrosilane used is 1 to 5 equivalents relative to 1 equivalent of a reactive end group of a fluorooxyalkylene group-containing polymer having a hydroxyl group at one end of the molecular chain and two olefin moieties at both ends of the molecular chain.
  • 1 to 2 equivalents more preferably about 1.2 equivalents can be used.
  • a platinum group metal catalyst such as rhodium, palladium, ruthenium or a boron catalyst
  • platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium
  • boron catalysts such as tris (pentafluorophenyl) borane, and the like can be given.
  • the dehydrogenation catalyst is used in an amount of 0.01 to 1 equivalent of a reactive end group of a fluorooxyalkylene group-containing polymer having a hydroxyl group at both ends of the molecular chain and two olefin moieties at both ends of the molecular chain. 0.0005 equivalent, more preferably 0.007 to 0.001 equivalent, and still more preferably about 0.005 equivalent can be used.
  • Solvents used for the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (14) include fluorine-containing aromatics such as 1,3-bis (trifluoromethyl) benzene and trifluoromethylbenzene as fluorine-based solvents.
  • Hydrocarbon solvents methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro- Hydrofluoroether (HFE) solvents such as 3-methoxy-2- (trifluoromethyl) pentane (trade name: Novec series, manufactured by 3M), perfluoro solvents composed of fully fluorinated compounds ( 3M, product name: Florinart series)
  • ether solvents such as tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used as the organic solvent.
  • the solvent is used in an amount of 10 to 300 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight of a fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain and having two olefin moieties at both ends of the molecular chain.
  • 150 parts by mass more preferably about 100 parts by mass can be used.
  • the solvent used is preferably a fluorinated solvent
  • the fluorinated solvent is 1,3-bis ( Trifluoromethyl) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5 , 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane and other hydrofluoroether (HFE) solvents (trade name: Novec series, manufactured by 3M), composed of fully fluorinated compounds Perfluoro solvent (made by 3M, trade name: Florinato Siri ), And the like.
  • HFE hydrofluoroether
  • the solvent is used in an amount of 10 to 300 parts by weight, preferably 50 to 150 parts by weight, more preferably about 100 parts by weight based on 100 parts by weight of the fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain. Mass parts can be used.
  • an organosilicon compound having a SiH group and a hydrolyzable end group in the molecule includes the following general formula: Compounds represented by (6) to (9) are preferred. (In the formula, R, X, n, R 1 , R 2 , R 3 , g, i, and j are the same as above.)
  • organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule examples include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, and triisopropenoxysilane. , Triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following organosilicon compounds.
  • a fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain and a SiH group in the molecule And the amount of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule when reacting with the organosilicon compound having a hydrolyzable end group has two olefin sites at both ends of the molecular chain.
  • 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, and still more preferably about 3 equivalents can be used per 1 equivalent of reactive end group of the fluorooxyalkylene group-containing polymer.
  • organosilicon having no hydrolyzable end groups in the molecule and having two or more SiH groups As the compound, compounds represented by the following general formulas (10) to (12) are preferable. (In the formula, R 1 , R 2 , g, j and i are the same as above.)
  • organosilicon compound having no hydrolyzable end group in the molecule and having two or more SiH groups examples include the following.
  • a fluoropolyether group-containing polymer-modified silane represented by the formula (1) where ⁇ is 2 the polymer is hydrolyzed with a fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain.
  • Amount of organosilicon compound having no hydrolyzable end group in the molecule and having two or more SiH groups in the molecule when reacting with an organosilicon compound having two or more SiH groups Is 5 to 20 equivalents, more preferably 7.5 to 12.5 equivalents, still more preferably 1 equivalent of a reactive end group of a fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain. About 10 equivalents can be used.
  • the organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule includes the following general formula:
  • the compound represented by (13) is preferred. (In the formula, R, X, V and n are the same as above.)
  • reaction product (intermediate) of an organosilicon compound having no ionic end group and having two or more SiH groups is reacted with an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule
  • the amount of the organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule includes a fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain and a hydrolyzable end group in the molecule.
  • 2 to 6 equivalents relative to 1 equivalent of the reactive end group of the reaction product (intermediate) with the organosilicon compound having two or more SiH groups can be used more preferably about 3 equivalents.
  • the hydrosilylation reaction catalyst may be platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum chloride
  • examples include complexes of acids with olefins, aldehydes, vinyl siloxanes, acetylene alcohols, and the like, and platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium.
  • platinum compounds such as vinylsiloxane coordination compounds.
  • the amount of hydrosilylation reaction catalyst used is a fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain, or two SiH groups without hydrolyzable end groups in the polymer and molecule. It is used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm in terms of transition metal (mass) with respect to the mass of the reaction product (intermediate) with the organosilicon compound.
  • the target compound can be obtained by depressurizingly distilling a solvent and an unreacted substance.
  • a fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain a compound represented by the following formula
  • trimethoxysilane is used as the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, a compound represented by the following formula is obtained.
  • the present invention further provides a surface treatment agent containing the fluoropolyether group-containing polymer-modified silane.
  • the surface treating agent is obtained by partially hydrolyzing a terminal hydrolyzable group of the above-mentioned fluoropolyether group-containing polymer-modified silane in advance by a known method, that is, a fluoro represented by the above formula (1). What hydrolyzed a part of X hydrolyzable group in the polyether group-containing polymer-modified silane to form a hydroxyl group can also be used.
  • the surface treatment agent may be a hydrolysis-condensation catalyst such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetran-butyl titanate, etc.), an organic acid (acetic acid, Methanesulfonic acid, fluorine-modified carboxylic acid, etc.) and inorganic acid (hydrochloric acid, sulfuric acid, etc.) may be added.
  • an organic tin compound dibutyltin dimethoxide, dibutyltin dilaurate, etc.
  • an organic titanium compound tetran-butyl titanate, etc.
  • an organic acid acetic acid, Methanesulfonic acid, fluorine-modified carboxylic acid, etc.
  • inorganic acid hydroochloric acid, sulfuric acid, etc.
  • the addition amount of the hydrolysis-condensation catalyst is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass with respect to 100 parts by mass of the fluoropolyether group-containing polymer-modified silane.
  • the surface treatment agent may contain a suitable solvent.
  • suitable solvents include fluorine-modified aliphatic hydrocarbon solvents (such as perfluoroheptane and perfluorooctane), fluorine-modified aromatic hydrocarbon solvents (such as 1,3-bis (trifluoromethyl) benzene), fluorine Modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (Petroleum benzine, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) can be exemplified.
  • fluorine-modified solvents are desirable in terms of solubility, wettability, and the like, and in particular, 1,3-bis (trifluoromethyl) benzene, perfluoro (2-butyltetrahydrofuran), perfluorotrimethyl. Butylamine and ethyl perfluorobutyl ether are preferred.
  • the above solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer-modified silane.
  • the optimum concentration of the fluoropolyether group-containing polymer-modified silane to be dissolved in the solvent varies depending on the treatment method and may be an amount that can be easily weighed. It is preferably 0.01 to 10% by mass, particularly 0.05 to 5% by mass with respect to the total mass of silane.
  • the total mass of the solvent and the fluoropolyether group-containing polymer-modified silane The content is preferably 1 to 100% by mass, particularly 3 to 30% by mass.
  • the surface treatment agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition.
  • the heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited.
  • the curing temperature varies depending on the curing method, for example, in the case of applying by vapor deposition, a range of 20 to 200 ° C. is desirable. Moreover, you may make it harden
  • the thickness of the cured coating is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm.
  • the substrate to be treated with the surface treating agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and oxide thereof, glass, plastic, ceramic, quartz and the like.
  • the surface treating agent of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for SiO 2 -treated glass or film.
  • Articles to be treated with the surface treatment agent of the present invention include car navigation, mobile phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, spectacle lenses, camera lenses, lens filters, sunglasses, Optical articles such as medical devices such as gastric cameras, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films. Since the surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the article and can further provide scratch resistance, it is particularly useful as a water / oil repellent layer for touch panel displays, antireflection films and the like. is there.
  • the surface treatment agent of the present invention is an antifouling coating for sanitary products such as bathtubs and washstands, window glass or tempered glass for automobiles, trains, airplanes, etc., antifouling coating for headlamp covers, etc.
  • Example 1 In a reaction vessel, 1,3-bis (trifluoromethyl) benzene 100 g, tris (pentafluorophenyl) borane 0.01 g (2.0 ⁇ 10 ⁇ 5 mol), the following formula (A) 100 g (2.7 ⁇ 10 ⁇ 2 mol) of a compound represented by the formula: After slowly dropping 13.6 g (3.3 ⁇ 10 ⁇ 2 mol) of silane represented by the formula, the mixture was stirred at 25 ° C. for 1 hour. Subsequently, water was added, and the lower fluorine compound layer was recovered by a liquid separation operation and then washed with acetone. The fluorine compound layer, which is the lower layer after washing, is recovered again, and the remaining solvent is distilled off under reduced pressure, whereby the following formula (C) 103 g of a fluoropolyether group-containing polymer represented by the formula:
  • Example 4 In a reaction vessel, 30 g of 1,3-bis (trifluoromethyl) benzene, 3.0 ⁇ 10 ⁇ 2 g of toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 8.2 ⁇ 10 ⁇ 7 mol as a simple substance of Pt), 9.0 g (4.5 ⁇ 10 ⁇ 2 mol) of tetramethyldisiloxane was mixed, and the following formula (K) After slowly dropping 30 g (9.0 ⁇ 10 ⁇ 3 mol) of the compound represented by the formula, the mixture was stirred at 25 ° C. for 1 hour. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 31 g of a liquid product.
  • Example 5 In a reaction vessel, 10 g of 1,3-bis (trifluoromethyl) benzene, 0.54 g (5.4 ⁇ 10 ⁇ 3 mol) of triethylamine, the following formula (A) 10 g (2.7 ⁇ 10 ⁇ 3 mol) of the compound represented by the formula: After slowly dropping 8.1 g (2.4 ⁇ 10 ⁇ 3 mol) of the compound represented by the formula, the mixture was stirred at 60 ° C. for 20 hours. Subsequently, hydrochloric acid was added, and the lower fluorine compound layer was recovered by a liquid separation operation, followed by washing with acetone. The fluorine compound layer, which is the lower layer after washing, is recovered again, and the remaining solvent is distilled off under reduced pressure, whereby the following formula (P) 17 g of a fluoropolyether group-containing polymer represented by the formula:

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Abstract

L'invention concerne : un silane modifié par un polymère contenant un groupe fluoropolyéther, le silane pouvant former une couche hydrofuge et oléofuge, présentant une excellente glissance ; un agent de traitement de surface comprenant le silane ; et un objet traité en surface présentant une surface traitée par l'agent de traitement de surface (c'est-à-dire un objet présentant, sur une surface correspondante, un film de revêtement durci formé à partir de l'agent de traitement de surface). Le silane modifié par un polymère contenant un groupe fluoropolyéther est représenté par la formule suivante (1). (Rf représente un résidu monovalent ou divalent d'un polymère contenant un groupe fluorooxyalkylène ; Y représente un groupe hydrocarboné divalent à hexavalent présentant éventuellement une liaison siloxane et/ou un groupe silylène ; R représente un groupe C1-4-alkyle ou un groupe phényle ; X représente un groupe hydroxy ou un groupe hydrolysable ; Q représente un groupe organique divalent présentant éventuellement une liaison siloxane et/ou un groupe silylène ; R' représente un groupe fluoroalkyle monovalent, un radical monovalent d'un polymère contenant un groupe fluorooxyalkylène, un groupe C1-4-alkyle ou un groupe phényle ; n représente un entier de 1 à 3 ; m représente un entier de 1 à 5 ; et α vaut 1 ou 2).
PCT/JP2016/080683 2015-12-14 2016-10-17 Silane modifié par un polymère contenant un groupe fluoropolyéther, agent de traitement de surface et objet WO2017104249A1 (fr)

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CN201680071632.4A CN108368253B (zh) 2015-12-14 2016-10-17 含有氟聚醚基的聚合物改性硅烷、表面处理剂和物品
JP2017556388A JP6642589B2 (ja) 2015-12-14 2016-10-17 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019065035A1 (fr) * 2017-09-27 2019-04-04 信越化学工業株式会社 Composition d'agent de revêtement fluoré, agent de traitement de surface, et article
CN114630871A (zh) * 2019-10-31 2022-06-14 信越化学工业株式会社 耐碱性拒水构件和该拒水构件的制造方法以及拒水构件的耐碱性和耐磨损性的提高方法
EP4071197A4 (fr) * 2019-12-03 2023-11-15 Shin-Etsu Chemical Co., Ltd. Polymère contenant un groupe fluoropolyéther, agent de traitement de surface et article
WO2024053354A1 (fr) * 2022-09-06 2024-03-14 信越化学工業株式会社 Polymère contenant du fluor, composition, agent de traitement de surface et article

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109913106B (zh) * 2019-03-14 2021-03-19 衢州氟硅技术研究院 一种表面防污处理剂组合物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1184103A (ja) * 1997-09-12 1999-03-26 Sony Corp 反射防止フィルター及びその製造方法
JP2014070164A (ja) * 2012-09-28 2014-04-21 Fujifilm Corp 表面改質剤、処理基材、化合物の製造方法、及び化合物
JP2014070163A (ja) * 2012-09-28 2014-04-21 Fujifilm Corp 表面改質剤、処理基材、化合物の製造方法、及び化合物
JP2015196723A (ja) * 2014-03-31 2015-11-09 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー
JP2015199906A (ja) * 2014-03-31 2015-11-12 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品
WO2016101185A1 (fr) * 2014-12-24 2016-06-30 E. I. Du Pont De Nemours And Company Perfluoropolyéthersilanes et leur procédé de préparation

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1869103B1 (fr) 2005-04-01 2017-05-03 Daikin Industries, Ltd. Modificateur de surface, article avec une surface modifiée, et procédée de modification
US8211544B2 (en) 2005-04-01 2012-07-03 Daikin Industries, Ltd. Surface modifier
CA2760801A1 (fr) * 2009-05-06 2010-11-11 3M Innovative Properties Company Dispositif d'inhalation medical
JP5235026B2 (ja) 2010-09-28 2013-07-10 信越化学工業株式会社 フルオロオキシアルキレン基含有ポリマー組成物および該組成物を含む表面処理剤並びに該表面処理剤で表面処理された物品
JP2012157856A (ja) 2011-01-13 2012-08-23 Central Glass Co Ltd 防汚性物品及びその製造方法
JP5857942B2 (ja) 2011-11-30 2016-02-10 信越化学工業株式会社 蒸着用フッ素系表面処理剤及び該表面処理剤で蒸着処理された物品
JP6260579B2 (ja) * 2015-05-01 2018-01-17 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品
JP6531833B2 (ja) * 2015-11-06 2019-06-19 信越化学工業株式会社 表面処理された樹脂製品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1184103A (ja) * 1997-09-12 1999-03-26 Sony Corp 反射防止フィルター及びその製造方法
JP2014070164A (ja) * 2012-09-28 2014-04-21 Fujifilm Corp 表面改質剤、処理基材、化合物の製造方法、及び化合物
JP2014070163A (ja) * 2012-09-28 2014-04-21 Fujifilm Corp 表面改質剤、処理基材、化合物の製造方法、及び化合物
JP2015196723A (ja) * 2014-03-31 2015-11-09 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー
JP2015199906A (ja) * 2014-03-31 2015-11-12 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品
WO2016101185A1 (fr) * 2014-12-24 2016-06-30 E. I. Du Pont De Nemours And Company Perfluoropolyéthersilanes et leur procédé de préparation

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019065035A1 (fr) * 2017-09-27 2019-04-04 信越化学工業株式会社 Composition d'agent de revêtement fluoré, agent de traitement de surface, et article
KR20200058409A (ko) * 2017-09-27 2020-05-27 신에쓰 가가꾸 고교 가부시끼가이샤 함불소 코팅제 조성물, 표면처리제 및 물품
KR102589656B1 (ko) * 2017-09-27 2023-10-16 신에쓰 가가꾸 고교 가부시끼가이샤 함불소 코팅제 조성물, 표면처리제 및 물품
CN114630871A (zh) * 2019-10-31 2022-06-14 信越化学工业株式会社 耐碱性拒水构件和该拒水构件的制造方法以及拒水构件的耐碱性和耐磨损性的提高方法
CN114630871B (zh) * 2019-10-31 2023-11-21 信越化学工业株式会社 耐碱性拒水构件和该拒水构件的制造方法以及拒水构件的耐碱性和耐磨损性的提高方法
EP4071197A4 (fr) * 2019-12-03 2023-11-15 Shin-Etsu Chemical Co., Ltd. Polymère contenant un groupe fluoropolyéther, agent de traitement de surface et article
WO2024053354A1 (fr) * 2022-09-06 2024-03-14 信越化学工業株式会社 Polymère contenant du fluor, composition, agent de traitement de surface et article

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