WO2009087981A1 - Composé polymérisable et procédé de production de ce dernier - Google Patents

Composé polymérisable et procédé de production de ce dernier Download PDF

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WO2009087981A1
WO2009087981A1 PCT/JP2009/000095 JP2009000095W WO2009087981A1 WO 2009087981 A1 WO2009087981 A1 WO 2009087981A1 JP 2009000095 W JP2009000095 W JP 2009000095W WO 2009087981 A1 WO2009087981 A1 WO 2009087981A1
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oco
och
group
oconh
nhconh
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PCT/JP2009/000095
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Japanese (ja)
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Masahiro Satoh
Atsushi Niwa
Satsuki Kitajima
Yuri Tomisaka
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Kri Inc.
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Priority to JP2009548908A priority Critical patent/JPWO2009087981A1/ja
Publication of WO2009087981A1 publication Critical patent/WO2009087981A1/fr

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    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/38—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atom of at least one amino group being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfones
    • C07C317/40—Y being a hydrogen or a carbon atom
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    • C07C317/00—Sulfones; Sulfoxides
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    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/38—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atom of at least one amino group being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfones
    • C07C317/42—Y being a hetero atom
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
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    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
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    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C07C323/40—Y being a hydrogen or a carbon atom
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    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C07C323/43—Y being a hetero atom
    • C07C323/44—X or Y being nitrogen atoms
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    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
    • C07C43/176—Unsaturated ethers containing halogen containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • 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 Table
    • 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
    • C07F7/1804—Compounds having Si-O-C linkages
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group

Definitions

  • the present invention relates to a polymerizable compound and a production method thereof. More specifically, the present invention relates to a polymerizable compound suitable for a surface treating agent and a production method thereof.
  • a polymerizable compound (silane coupling agent) represented by ⁇ n is a positive number from 1 to 12 ⁇ is known.
  • An object of the present invention is to provide a polymerizable compound that can be obtained ⁇ simply in a short time ⁇ more easily.
  • Rf is a polyfluoroalkyl group which may contain an ether bond
  • R 1 is a direct bond
  • R 2 is a direct bond, and has 1 to 4 carbon atoms.
  • An alkylene group of 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, R 3 may be a direct bond, a urethane bond or a urea bond, an alkylene group having 1 to 15 carbon atoms or an arylene group having 6 to 20 carbon atoms,
  • X 0 and X 2 is a direct bond or a group represented by —O—, —S— or —NH—
  • X 1 is a direct bond or a group represented by —S—, —SO 2 —, —O—, —NH— or> N—.
  • Z is a trialkoxysilyl group, a monomethyl dialkoxysilyl group, a trihalogenosilyl group, a (meth) acryloxy group, a (meth) acryloylamino group, a vinyl group or a 1-methylvinyl group.
  • a polymerizable group C is a carbon atom, O is an oxygen atom, N is a nitrogen atom, S is a sulfur atom, H is a hydrogen atom, q is 0 or 1 (where q is 0 and Z is a (meth) acryloxy group or In the case of a (meth) acryloylamino group, R 3 includes a urethane bond or a urea bond.), T and r are 0 or 1, and m is 1 or 2.
  • Rf is a polyfluoroalkyl group which may contain an ether bond
  • R 4 and R 6 are alkylene groups having 1 to 4 carbon atoms or arylene groups having 6 to 10 carbon atoms
  • R 5 is ethylene or 1-methylethylene
  • R 7 is methyl
  • X is a group represented by —S—, —O—, —NH— or> N—
  • Y is an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group or a halogen atom
  • C is a carbon atom
  • O is An oxygen atom
  • N is a nitrogen atom
  • S is a sulfur atom
  • H is a hydrogen atom
  • Si is a silicon atom
  • m is 1 or 2
  • n is 0 or 1.
  • the feature of the surface treating agent of the present invention is that it contains the polymerizable compound described above.
  • a feature of the production method of the present invention is a method for producing the above polymerizable compound, A reaction step (1-1) of reacting a polyfluoroalkyl (meth) acrylate with a mercapto group-containing alkoxysilane or an amino group-containing alkoxysilane; Reaction of (meth) acrylic acid polyfluoroalkyl ester with mercapto group-containing alcohol, mercapto group-containing phenol, amino group-containing alcohol, amino group-containing phenol or mercapto group-containing amine, or halogenated polyfluoroalkyl and mercapto group-containing alcohol , A mercapto group-containing phenol, an amino group-containing alcohol, an amino group-containing phenol, or a mercapto group-containing amine, or a reaction between a halogenated polyfluoroalkyl and a thiolizing agent or an aminating agent.
  • reaction step (2-1) of reacting a polyfluoroalkylalkanol, polyfluoroalkylamine or polyfluorothiol the polyfluoroalkyl alcohol, polyfluoroalkylphenol, polyfluorothiol Reaction step of reacting alkylamine or polyfluorothiol with isocyanato group-containing (meth) acrylate or isocyanato group-containing alkoxysilane, chloromethyl group-containing (meth) acrylate, chloromethyl group-containing styryl group or chloromethyl group-containing alkoxysilane ( 1-2), Reaction step (1-3) of reacting polyfluoroalkyl alcohol, polyfluoroalkylphenol, polyfluoroalkylamine or polyfluorothiol with (meth) acrylic acid, (meth) acrylic acid halide or (meth) acrylic anhydride , A reaction step (2-1) of reacting a polyfluoroalkylalkanol, polyfluor
  • the gist of the feature of the method for producing a surface-treated product of the present invention is that it includes the step of treating the surface-treating agent on the material to be treated.
  • the polymerizable compound of the present invention can be obtained ⁇ simply in a short time ⁇ more easily.
  • the surface treating agent of the present invention can modify the surface of a substance more easily ⁇ in a short time, easily ⁇ . Further, the surface treatment agent of the present invention has an advantage that there is no problem in terms of safety (toxicity and the like). According to the production method of the present invention, a polymerizable compound can be obtained more simply ⁇ simply in a short time ⁇ .
  • the production method of the present invention uses a raw material excellent in safety (toxicity), there is an advantage that there is no problem in terms of safety (toxicity).
  • polyfluoroalkyl group (Rf) that may contain an ether bond
  • examples of the polyfluoroalkyl group (Rf) that may contain an ether bond include a polyfluoroalkyl group having 1 to 20 carbon atoms, and some of the fluorine atoms may be substituted with hydrogen atoms.
  • Examples of the polyfluoroalkyl group (Rf) that may contain an ether bond include a trifluoromethyl group (CF 3- ), a perfluoroethyl group (C 2 F 5- ), and a perfluoropropyl group (including linear and branched).
  • the alkylene group includes a methylene group (—CH 2 —), a thiomethylene group (—SCH 2 —), and a sulfoxide methylene group.
  • a phenylene group (—C 6 H 4 —), a thiophenylene group (—SC 6 H 4 —), a sulfoxide phenylene group (—SO 2 C 6 H 4 —), a methylene phenylene group (—CH 2 C 6 H 4 —), ethylene phenylene group (—CH 2 CH 2 C 6 H 4 —), phenylene bis (methylene) group (—CH 2 C 6 H 4 CH 2 —) and phenylene bis (ethylene) group ( -CH 2 CH 2 C 6 H 4 CH 2 CH 2 -) and the like.
  • the alkylene group includes a methylene group (—CH 2 —), an ethylene group (—CH 2 CH 2 —), and 1 -Methylethylene group (-CH (CH 3 ) CH 2- ) and the like can be mentioned.
  • arylene group examples include a methylene phenylene group (—CH 2 C 6 H 4 —), a methylene phenylene ethylene group (—CH 2 C 6 H 4 CH 2 CH 2 —), and a methylene phenylene oxymethylene phenylene group (—CH 2 C 6 H 4 OCH 2 C 6 H 4 —) and the like.
  • the alkylene group includes a methylene group (—CH 2 —), an ethylene group ( -CH 2 CH 2- ), trimethylene group (-CH 2 CH 2 CH 2- ), 1-methylethylene group (-CH (CH 3 ) CH 2- ), tetramethylene group (-CH 2 CH 2 CH 2 CH 2 -), 2-methyltrimethylene group (-CH 2 CH (CH 3) CH 2 -), 5- aza-3-oxa-4-Okisohepuchiren group (-CH 2 CH 2 OCONHCH 2 CH 2 -), 5 -Aza-3-oxa-4-oxooctylene group (-CH 2 CH 2 OCONHCH 2 CH 2 CH 2- ), 3-aza-5-oxa-4-oxooctylene group (-CH 2 CH 2 CH 2 O CONHCH 2 CH 2 CH 2- ), 3-aza-5-oxa-4-oxooctylene group (-CH 2 CH 2 CH 2 O CONHCH 2 CH 2 CH 2- ), 3-aza-5-ox
  • the arylene group includes a phenylene group (—C 6 H 4 —), an oxymethylene phenylene group (—OCH 2 C 6 H 4 —), and an oxymethylene phenylethylene group (—OCH 2 C 6 H 4 CH 2 —).
  • Oxymethylene phenylene ethylene group (—OCH 2 C 6 H 4 CH 2 CH 2 —), methylene phenylene group (—CH 2 C 6 H 4 —), ethylene phenylene group (—CH 2 CH 2 C 6 H 4 — ), Phenylenemethylene group (—C 6 H 4 CH 2 —), phenyleneethylene group (—C 6 H 4 CH 2 CH 2 —), phenylenebis (methylene) group (—CH 2 C 6 H 4 CH 2 —) , A group represented by a phenylenebis (ethylene) group (—CH 2 CH 2 C 6 H 4 CH 2 CH 2 —), —C 6 H 4 —CH 2 CH 2 SCH 2 CH 2 CH 2 —, —C 6 H 4 -O ONH-CH 2 CH 2 - group represented by, -C 6 H 4 -OCONH-CH 2 CH 2 CH 2 - group represented by, -C 6 H 4 -NHCONH-CH 2 CH 2 - is represented by A group represented by
  • the trialkoxy group and the alkoxy group of the monomethyl dialkoxy group include alkoxy groups having 1 to 4 carbon atoms (methoxy, ethoxy, n-propoxy, iso-propoxy, tert-butoxy, etc.).
  • (Meth) acryl ! means “acryl ## or "methacryl ## (hereinafter the same).
  • Rf and m are the same as those in the formula (1) or (2).
  • R 4 and R 6 are the same as the alkylene group having 1 to 4 carbon atoms or the arylene group having 6 to 10 carbon atoms in R 1 in the formula (1) or (2).
  • alkoxy groups having 1 to 3 carbon atoms examples include methoxy, ethoxy, n-propoxy, iso-propoxy, tert-butoxy and the like.
  • a polymerizable compound represented by the formula (1) ⁇ including a polymerizable compound (silicon compound) represented by the formula (3).
  • ⁇ Includes, for example, compounds represented by the following chemical formula.
  • C 6 F 13 —CH 2 CH 2 —OCO—CH 2 CH 2 —S—CH 2 CH 2 CH 2 —OCO—CH ⁇ CH 2 C 6 F 13 -CH 2 CH 2 -OCO-CH 2 CH 2 -S-CH 2 CH 2 CH 2 -OCO-C (CH 3) CH 2 C 6 F 13 —CH 2 CH 2 —OCO—CH 2 CH 2 —S—CH 2 CH 2 —OCONH—CH 2 CH 2 —OCO—CH ⁇ CH 2 C 6 F 13 —CH 2 CH 2 —OCO—CH 2 CH 2 —S—C 6 H 4 —OCONH—CH 2 CH 2 —OCO—CH ⁇ CH 2 C 6 F 13 —CH 2 CH 2 —OCO—CH 2 CH 2 —S—CH 2 CH 2 —OCONH—CH 2 CH 2 —OCO—C (CH 3 ) ⁇ CH 2 C 6 F 13 -CH 2 CH 2 -OCO-CH 2 CH 2 -S-C 6 H 4 -OCON
  • C 6 F 13 —CH 2 CH 2 —OCO—CH 2 CH 2 —S—CH 2 CH 2 —NHCONH—CH 2 CH 2 —OCO—CH ⁇ CH 2 C 6 F 13 —CH 2 CH 2 —OCO—CH 2 CH 2 —S—C 6 H 4 —NHCONH—CH 2 CH 2 —OCO—CH ⁇ CH 2 C 6 F 13 —CH 2 CH 2 —OCO—CH 2 CH 2 —S—CH 2 CH 2 —NHCONH—CH 2 CH 2 —OCO—C (CH 3 ) ⁇ CH 2 C 6 F 13 -CH 2 CH 2 -OCO-CH 2 CH 2 -S-C 6 H 4 -NHCONH-CH 2 CH 2 -OCO-C (CH 3) CH 2 C 6 F 13 -CH 2 CH 2 -OCO-CH (CH 3) CH 2 -SO 2 -CH 2 CH 2 CH 2 -Si (OCH 3) 3 C 6 F 13 -CH 2 CH 2 -OCO-CH 2
  • the polymerizable compound of the present invention can be easily obtained by a known production method.
  • the method for producing a polymerizable compound ⁇ polymerizable compound represented by the formula (3) ⁇ represented by the formula (1) and the polymerizable group (Z) being a trialkoxysilyl or monomethyl dialkoxy group includes (meth) Reaction step (1-1) of reacting polyfluoroalkyl ester of acrylic acid with mercapto group-containing alkoxysilane or amino group-containing alkoxysilane ⁇ alkoxysilylalkanethiol, alkoxysilylalkylamine, alkoxysilylarylthiol or alkoxysilylarylamine ⁇ ) Is preferably included.
  • a reaction solvent may be used.
  • the reaction solvent is not particularly limited as long as it does not react with the above compound group ⁇ (meth) acrylic acid polyfluoroalkyl ester, etc. ⁇ and dissolves these.
  • ether diethyl ether, tetrahydrofuran, 1,2- Dimethoxyethane, dioxane, etc. ⁇
  • alcohol ⁇ methyl alcohol, ethyl alcohol, propyl alcohol, etc. ⁇
  • ketone ⁇ acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. ⁇
  • aprotic solvent ⁇ N, N-dimethylformamide, N, N-dimethylacetamide N-methylpyrrolidone, dimethyl sulfoxide, etc. ⁇ and hydrocarbons ⁇ hexane, octane, benzene, toluene, xylene, etc. ⁇ and the like.
  • a known radical initiator ⁇ azo-based initiator for example, 2,2′-azobisisobutyronitrile
  • peroxide-based initiator for example, benzoyl peroxide
  • alkoxyalkanethiol it is preferable to use a radical initiator or to advance the reaction by light irradiation.
  • the reaction temperature in the reaction step (1-1) is not limited as long as radical addition or Michael addition proceeds, and is, for example, ⁇ 10 to 200 ° C. (preferably 0 to 150 ° C., more preferably 20 to 130 ° C., particularly preferably 60 to 120 ° C.).
  • the production method of the polymerizable compound represented by the formula (1) includes (meth) acrylic acid polyfluoroalkyl ester and mercapto group-containing alcohol, mercapto group-containing phenol, amino group-containing alcohol, amino group-containing phenol or mercapto group-containing. Reaction with an amine (including a mercapto group-containing amine salt such as hydrochloride) or a polymerizable compound in which q in the formula (1) is 1 is obtained.
  • a halogenated polyfluoroalkyl with a mercapto group-containing alcohol, a mercapto group-containing phenol, an amino group-containing alcohol, an amino group-containing phenol, or a mercapto group-containing amine (including a mercapto group-containing amine salt such as a hydrochloride) Or reacting a halogenated polyfluoroalkyl with a thiolating agent (eg, thiourea) or an aminating agent (eg, sodium azide) to produce a polyfluoroalkyl alcohol, polyfluoroalkylphenol, polyfluoroalkylamine or polyfluoro After obtaining the thiol, the polyfluoroalkyl alcohol, polyfluoroalkylphenol, polyfluoroalkylamine or polyfluorothiol and the isocyanate group-containing (meth) acrylate or isocyanate Isocyanatomethyl group-containing alkoxys
  • reaction conditions of the (meth) acrylic acid polyfluoroalkyl ester and the mercapto group-containing alcohol, mercapto group-containing phenol, amino group-containing alcohol or amino group-containing phenol are the same as those in the reaction step (1-1).
  • the halogenated polyfluoroalkyl is a perfluorobutyl iodide.
  • the reaction is carried out at room temperature (about 20 to 30 ° C.) in the presence of sodium formate and sodium sulfite in a solvent in which these reagents are dissolved (for example, water / dimethylformamide mixed solvent).
  • a solvent in which these reagents are dissolved for example, water / dimethylformamide mixed solvent.
  • halogenated polyfluoro compound is a partially fluorinated product such as 2-perfluorobutylethyl iodide
  • a base a mercapto group-containing alcohol, a mercapto group-containing phenol, an amino group-containing alcohol, an amino group-containing phenol
  • a corresponding alcohol, phenol or amine can be obtained by reacting with a mercapto group-containing amine (including a mercapto group-containing amine salt such as hydrochloride).
  • the halogenated polyfluoro compound is a partially fluorinated compound such as 2-perfluorobutylethyl iodide
  • the corresponding amine can be obtained by reacting with sodium azide and reducing with hydrogen.
  • the halogenated polyfluoro compound is a partially fluorinated product such as 2-perfluorobutylethyl iodide
  • the corresponding thiol can be obtained by the action of thiourea and hydrolysis.
  • an appropriate oxidizing agent m-chloroperbenzoic acid or the like
  • an appropriate solvent methylene chloride or the like
  • a reaction solvent may be used in the case of (thio) urethanation or ureaation reaction.
  • the reaction solvent is not limited as long as it does not react with the above compound group ⁇ isocyanato group-containing (meth) acrylate, etc. ⁇ and dissolves these.
  • ether diethyl ether, tetrahydrofuran, 1,2-dimethoxy Ethane and dioxane, etc. ⁇
  • ketones ⁇ acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. ⁇
  • aprotic solvents ⁇ N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, etc. ⁇ and hydrocarbons ⁇ Hexane, octane, benzene, toluene, xylene and the like ⁇ .
  • reaction step (1-2) In the case of (thio) urethanation or ureaation reaction in the reaction step (1-2), a known reaction catalyst for promoting the (thio) urethanation reaction or urealation reaction ⁇ tin compound (for example, di-n-butyltin dilaurate) ) And a tertiary amine (for example, triethylamine) ⁇ .
  • a known reaction catalyst for promoting the (thio) urethanation reaction or urealation reaction ⁇ tin compound (for example, di-n-butyltin dilaurate) )
  • a tertiary amine for example, triethylamine
  • the reaction temperature is not limited as long as the (thio) urethanation reaction or urealation reaction proceeds, for example, ⁇ 10 to 200 ° C. (preferably Is about 0 to 150 ° C., more preferably 20 to 130 ° C., particularly preferably 20 to 110 ° C.).
  • reaction solvent is not limited as long as it does not react with the above compound group ⁇ chloromethylphenyl group-containing (meth) acrylate, chloromethylphenyl group-containing vinyl, chloromethylphenyl group-containing alkoxysilane, etc. ⁇ and dissolves these.
  • ether diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, dioxane, etc. ⁇
  • alcohol ⁇ methyl alcohol, ethyl alcohol, isopropyl alcohol, etc. ⁇
  • ketone ⁇ acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. ⁇
  • aprotic Solvents ⁇ N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, etc. ⁇ and hydrocarbons ⁇ hexane, octane, benzene, toluene, xylene, etc. ⁇
  • a base for example, sodium hydroxide, potassium hydroxide, triethylamine, etc.
  • a base for example, sodium hydroxide, potassium hydroxide, triethylamine, etc.
  • the reaction temperature is not limited as long as the (thio) etherification reaction proceeds, for example, ⁇ 10 to 200 ° C. (preferably 0 to 150 ° C., more preferably 20 To about 130 ° C., particularly preferably about 20 to 110 ° C.).
  • a reaction solvent may be used.
  • the reaction solvent is not limited as long as it does not react with the above compound group ⁇ (meth) acrylic acid, (meth) acrylic acid halide or (meth) acrylic anhydride, etc. ⁇ and dissolves these, for example, , Ether ⁇ diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, dioxane and the like ⁇ , aprotic solvent ⁇ N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, etc. ⁇ and hydrocarbons ⁇ Hexane, octane, benzene, toluene, xylene, etc. ⁇ and the like.
  • an acid sulfuric acid, hydrochloric acid, paratoluenesulfonic acid, etc.
  • a condensing agent dicyclohexylcarbodiimide, azodiethylcarboxylic acid / triphenylphosphine, etc.
  • the reaction temperature in the reaction step (1-3) is not limited as long as the esterification reaction or amidation reaction proceeds.
  • the reaction temperature is -10 to 200 ° C (preferably 0 to 150 ° C, more preferably 20 to 130 ° C, particularly The temperature is preferably about 20 to 110 ° C.
  • the polymerizable compound having a sulfone in the molecule acts on the polymerizable compound having the corresponding thioether in an appropriate solvent (such as methylene chloride) with an appropriate oxidizing agent (such as m-chloroperbenzoic acid). Can also be obtained.
  • an appropriate solvent such as methylene chloride
  • an appropriate oxidizing agent such as m-chloroperbenzoic acid
  • a reaction of reacting a polyfluoroalkylalkanol or polyfluoroalkylamine with an isocyanato group-containing alkoxysilane or an isocyanato group-containing (meth) acrylate It is preferable to include the step (2-1).
  • reaction solvent is not limited as long as it does not react with the above compound group ⁇ isocyanato group-containing alkoxysilane or isocyanato group-containing (meth) acrylate, etc. ⁇ and dissolves them.
  • ether diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, dioxane, etc. ⁇
  • ketones ⁇ acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. ⁇
  • aprotic solvents ⁇ N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, etc.
  • hydrocarbons ⁇ hexane, octane, benzene, toluene, xylene, etc. ⁇ and the like.
  • the reaction step (2-1) includes a known reaction catalyst ⁇ tin compound (for example, di-n-butyltin dilaurate) and tertiary amine (for example, triethylamine) that promotes (thio) urethanation or urealation reaction. ) Etc. ⁇ .
  • ⁇ tin compound for example, di-n-butyltin dilaurate
  • tertiary amine for example, triethylamine
  • the reaction temperature in the reaction step (2-1) is not limited as long as the (thio) urethane reaction or urea reaction proceeds, and is, for example, ⁇ 10 to 200 ° C. (preferably 0 to 150 ° C., more preferably 20 to 130 ° C.). ° C, particularly preferably 20 to 110 ° C.
  • a reaction step (2-2) of reacting (meth) acrylic acid polyfluoroalkyl ester with trialkoxysilane or trihalogenated silane It is preferable to contain.
  • a reaction solvent may be used.
  • the reaction solvent is not particularly limited as long as it does not react with the above compound group ⁇ (meth) acrylic acid polyfluoroalkyl ester, etc. ⁇ and dissolves these.
  • ether diethyl ether, tetrahydrofuran, 1,2- Dimethoxyethane, dioxane, etc. ⁇
  • ketones ⁇ acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. ⁇
  • esters ⁇ ethyl acetate, propyl acetate, butyl acetate, etc. ⁇
  • aprotic solvents ⁇ N, N-dimethylformamide, N, N-dimethylacetamide N-methylpyrrolidone, dimethyl sulfoxide, etc. ⁇ and hydrocarbons ⁇ hexane, octane, benzene, toluene, xylene, etc. ⁇ and the like.
  • reaction step (2-2) a known reaction catalyst for promoting hydrosilylation reaction ⁇ platinum compound (for example, potassium hexachloroplatinum (IV)), etc .; and radical initiator (for example, azobisisobutyronitrile, etc.) ) Is preferably used.
  • platinum compound for example, potassium hexachloroplatinum (IV)
  • radical initiator for example, azobisisobutyronitrile, etc.
  • the reaction temperature in the reaction step (2-2) is not limited as long as the hydrosilylation reaction proceeds, and is, for example, ⁇ 10 to 200 ° C. (preferably 0 to 150 ° C., more preferably 20 to 130 ° C., particularly preferably 20 About 110 ° C).
  • the polymerizable compound of the present invention can be applied to a surface treatment agent (modifier) and the like, and is suitable, for example, as a silane coupling agent or a coating agent.
  • the surface treatment agent of the present invention may contain the above-described polymerizable compound, but when the polymerizable group (Z) of the polymerizable compound is a trialkoxysilyl group or a monomethyl dialkoxysilyl group, other than the above-described polymerizable compound
  • Metal alkoxide ⁇ metal alkoxide oligomer including partial hydrolyzate; for example, alkoxysilane ⁇ , metal oxide sol (for example, silica sol) and / or metal oxide fine particles (for example, silicon oxide fine powder). But you can.
  • Examples of the metal of the metal alkoxide include silicon, titanium, zirconium and aluminum. Of these, silicon, titanium and zirconium are preferred, and silicon is more preferred.
  • alkoxy group of the metal alkoxide examples include an alkoxy group having 1 to 10 carbon atoms ⁇ methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy and the like ⁇ . Of these, methoxy, ethoxy, isopropoxy, n-butoxy and t-butoxy are preferred, and methoxy and ethoxy are more preferred.
  • a part of the alkoxy group (1 or 2) is another organic group ⁇ methyl group, 3-aminopropyl group, 3-glycidyloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, alkanoyloxy group (Such as acetoxy, propanoyloxy, butanoyloxy, hexanoyloxy, 2-ethylhexanoyloxy, acryloxy and methacryloxy) and ⁇ -diketonate groups (2,4-pentanedionate, trifluoropentanedionate, hexafluoropentane) Dioneate and 2,2,6,6-tetramethyl-3,5-heptanedionate etc.), etc. ⁇ may be substituted.
  • Examples of the metal of the metal oxide sol include silicon, titanium, zirconium and aluminum. Of these, silicon, titanium and zirconium are preferred, and silicon is more preferred.
  • metal oxide sol examples include silica sol ⁇ Snowtex series manufactured by Nissan Chemical Co., Ltd. ⁇ .
  • silicon dioxide fine particles silicon dioxide fine particles ⁇ Aerosil series manufactured by Nippon Aerosil Co., Ltd., etc .; "Aerosil” is a registered trademark of Degussa Aktiengesellschaft. ⁇ .
  • the total content (wt%) thereof is preferably 1 to 90, more preferably 5 based on the weight of the polymerizable compound. To 80, particularly preferably 5 to 70.
  • the surface treatment agent of the present invention further improves workability (handleability, paintability, etc.).
  • a diluting solvent may be included.
  • the diluting solvent is not limited as long as it does not react with the polymerizable compound, metal alkoxide, metal oxide sol and metal oxide fine particles of the present invention and dissolves or disperses them.
  • ether ⁇ tetrahydrofuran and dioxane Etc. ⁇ alcohol ⁇ methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol etc. ⁇
  • the content of the dilution solvent is not limited.
  • the content of the dilution solvent may be the polymerizable compound, metal alkoxide, metal of the present invention.
  • the content of the oxide sol and metal oxide fine particles is 0.0001 to 10% by weight based on the total weight of the polymerizable compound of the present invention, metal alkoxide, metal oxide sol, metal oxide fine particles and dilution solvent ( The amount is preferably 0.0001 to 5% by weight, particularly preferably 0.0001 to 2% by weight.
  • the surface treatment agent of the present invention may contain the polymerizable compound of the present invention as it is. From the viewpoint of film properties and the like, it is preferable to hydrolyze the polymerizable compound. When hydrolyzing, a catalyst may be added to promote hydrolysis.
  • Catalysts include acids ⁇ inorganic acids (such as hydrochloric acid, sulfuric acid and nitric acid) and organic acids (such as formic acid, acetic acid and butyric acid) ⁇ and bases ⁇ inorganic bases (such as ammonia, sodium hydroxide and potassium hydroxide) and organic bases ( Triethylamine, diethylamine, monoethylamine, 3-aminopropyltrimethoxysilane, etc.) ⁇ and the like.
  • acids ⁇ inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid
  • organic acids such as formic acid, acetic acid and butyric acid
  • bases ⁇ inorganic bases (such as ammonia, sodium hydroxide and potassium hydroxide) and organic bases ( Triethylamine, diethylamine, monoethylamine, 3-aminopropyltrimethoxysilane, etc.) ⁇ and the like.
  • the amount of water added is preferably 1 to 1000, more preferably 5 to 500, particularly preferably 10 based on the number of moles of the polymerizable compound (silicon compound) of the present invention. ⁇ 300.
  • the surface treatment agent of the present invention includes a metal alkoxide and a metal oxide.
  • the sol, metal oxide fine particles and / or solvent are included, the surface treatment agent of the present invention uniformly mixes the above polymerizable compound and the metal alkoxide, metal oxide sol, metal oxide fine particles and / or solvent. Can be obtained.
  • hydrolyzing the above polymerizable compound when hydrolyzing the above polymerizable compound, it may be hydrolyzed before being uniformly mixed with the metal alkoxide, metal oxide sol, metal oxide fine particles and / or solvent, or may be hydrolyzed after being uniformly mixed. Also good.
  • polymerizable group (Z) of the polymerizable compound is a (meth) acryloyl group or a vinyl group
  • other polymerizable compounds may be included in addition to the polymerizable compound.
  • Examples of other polymerizable compounds include (meth) acrylic monomers, imide monomers, unsaturated carboxylic acids, aromatic vinyl monomers, vinyl ether monomers, fatty acid vinyl monomers, and crosslinking monomers. Is included.
  • (meth) acrylic monomers examples include alkyl (1 to 30 carbon atoms) (meth) acrylate ⁇ methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) acrylate, etc. ⁇ , cyclo Alkyl (3 to 8 carbon atoms) (meth) acrylate ⁇ cyclohexyl (meth) acrylate, etc. ⁇ , (meth) acrylate having a monocyclic heterocyclic hydrocarbon group (2 to 10 carbon atoms) ⁇ oxacycloalkyl (meta ) Acrylate; for example, glycidyl (meth) acrylate and tetrahydro (meth) acrylate ⁇ , (meth) acrylate having a bridged alicyclic hydrocarbon group (3 to 8 carbon atoms) ⁇ bicycloalkyl (meth) acrylate, tricycloalkyl (Meth) acrylate,
  • imide monomers examples include maleimide, N-alkyl (C1-4) maleimide ⁇ N-methylmaleimide, N-ethylmaleimide, etc. ⁇ and N-aryl (C6-10) maleimide ⁇ N-phenylmaleimide, etc. ⁇ Etc. are mentioned.
  • Examples of the unsaturated carboxylic acid include crotonic acid, maleic acid, maleic anhydride and itaconic acid.
  • aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, pt-butylstyrene, vinyltoluene and the like.
  • vinyl ether monomers examples include vinyl methyl ether and vinyl ethyl ether.
  • fatty acid vinyl ester monomer examples include vinyl acetate and vinyl propionate.
  • crosslinking monomers include diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, hydroxymethyl (meth) acryl acrylate, hydroxyethyl (meth) acryl acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, Examples thereof include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, butadiene, chloroprene, glycidyl (meth) acrylate, and isocyanatoethyl (meth) acrylate.
  • the polymerizable group (Z) of the polymerizable compound is a (meth) acryloyl group or a vinyl group
  • the polymerizable compound (and other polymerizable compound) is preferably used as a polymer from the viewpoint of film-forming properties. Either solution polymerization or emulsion polymerization can be obtained.
  • the polymer may be any of a random copolymer, a block copolymer, and a graft copolymer.
  • polymers can be obtained by ordinary radical reactions using ordinary radical initiators (AIBN: azobisisobutyronitrile, BPO: benzoyl peroxide, etc.), but living radical polymerization (living radicals by nitroxyl) Polymerization, living radical polymerization using a transition metal complex catalyst, living radical polymerization using an iniferter method, etc.).
  • AIBN azobisisobutyronitrile
  • BPO benzoyl peroxide, etc.
  • living radical polymerization living radicals by nitroxyl
  • emulsion polymerization it can be obtained by radical reaction after emulsifying a polymerizable compound in water in the presence of a polymerization initiator and an emulsifier.
  • the polymerization initiator oil-soluble ones such as AIBN and BPO, and water-soluble ones such as azobisisobutylamidine dihydrochloride, potassium persulfate, and ammonium persulfate can be used.
  • the content (% by weight) thereof is preferably 0.01 to 90, more preferably 0.01 to 80, particularly preferably based on the weight of the polymerizable compound. 0.01 to 70.
  • the surface treatment agent has a diluent solvent for improving workability (handling property, paintability, etc.). May be included.
  • diluent solvent dissolves such as ether ⁇ tetrahydrofuran and dioxane, etc. ⁇ , alcohol ⁇ methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, etc. ⁇ , ketone ⁇ Acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. ⁇ , ester ⁇ ethyl acetate, propyl acetate, butyl acetate, etc. ⁇ , aprotic solvent ⁇ N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide Etc. ⁇ , fluorine-based compounds ⁇ hexafluorohexanol and the like ⁇ and hydrocarbons ⁇ hexane, octane, benzene, toluene, xylene and the like
  • the content of the diluting solvent is not limited, and the content of the diluting solvent is, for example, the polymerizable compound of the present invention and other polymerizable compounds.
  • the compound content is 0.01 to 30% by weight (preferably 0.1 to 25% by weight, particularly preferably 0.1% by weight) based on the total weight of the polymerizable compound of the present invention, the other polymerizable compound and the diluent solvent. 2 to 20% by weight).
  • the form of the surface treatment agent of the present invention is not limited, but a solution, emulsion or aerosol is preferred. A known method or the like can be applied to each form.
  • a known method for example, a method of spraying the surface treatment agent on the treatment body or spraying the surface treatment agent on the treatment body
  • a method of immersing an object to be treated or an object to be treated in a surface treatment agent can be applied.
  • the amount of the surface treatment agent used may be appropriately determined depending on the material of the surface treatment body, the purpose of use, and the like.
  • Materials to be treated include textile products (carpets, clothes, umbrellas, etc.), stones, filters (electrostatic filters, etc.), dust masks, fuel cells, glass (vehicle windshields, vehicle side mirrors, etc.), paper, wood , Leather (shoes and bags, etc.), fur, asbestos, brick, cement, metal, metal oxide, ceramic products, plastics, painted bodies, plaster, and the like.
  • Textile materials include natural fibers (cotton, hemp, wool, silk, etc.), synthetic fibers (polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc.), semi-synthetic fibers (rayon, acetate, etc.) , Inorganic fibers (glass fibers, carbon fibers, asbestos fibers, etc.) and mixed fibers thereof.
  • the reaction is carried out at reflux temperature for 17 hours under an argon atmosphere, and the polymerizable compound (1) ⁇ 3-((3-trimethoxysilyl) propylthio) propionic acid 2- (perfluorooctyl) ethyl of the present invention; C 8 F 17
  • a MEK solution containing —CH 2 CH 2 —OCO—CH 2 CH 2 —S—CH 2 CH 2 CH 2 —Si (OCH 3 ) 3 ⁇ was obtained.
  • Example 2 2- (Perfluorooctyl) ethyl acrylate (Daikin Industries, Ltd.) 7.0 parts (13.5 mmol parts) and 3- (trimethoxysilyl) propylamine (Chisso Corporation) 1.2 parts (6.70) Mmole) was dissolved in 73.8 parts of MEK and reacted at reflux temperature for about 48 hours under an argon atmosphere to obtain the polymerizable compound (2) ⁇ N- (3-trimethoxysilyl) propyl-3 of the present invention.
  • Example 3 2-perfluorooctylethanol (Daikin Kogyo Co., Ltd.) 12.5 parts (26.9 mmol parts), 3- (triethoxysilyl) propyl isocyanate (Chisso Corporation) 6.65 parts (26.9 mmol parts) And 0.01 part of di-n-butyltin dilaurate were dissolved in 170 parts of dehydrated MEK and reacted at about 25 ° C.
  • Example 4 2- (perfluorobutyl) ethyl methacrylate (Daikin Kogyo Co., Ltd.) 8 parts (24.1 mmol), 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) 4.73 parts (24. 1 mmol part) and 2,2′-azobisisobutyronitrile 198 ⁇ 10 ⁇ 3 parts (0.12 mmol part) were dissolved in 115 parts of MEK and then reacted at reflux temperature for 17 hours under an argon atmosphere.
  • Example 5 2- (perfluorohexyl) ethyl acrylate (Daikin Kogyo Co., Ltd.) 5.64 parts (13.5 mmol parts), 3- (trimethoxysilyl) propylamine (Chisso Corporation) 1.2 parts (6.7 Mmol part) was dissolved in 61.6 parts of MEK and reacted at reflux temperature for 48 hours under an argon atmosphere to obtain the polymerizable compound (5) ⁇ N- (3-trimethoxysilyl) propyl-3, 3′-iminodipropionic acid bis 2- (perfluorohexyl) ethyl; (C 6 F 13 —CH 2 CH 2 —OCO—CH 2 CH 2 —) 2 N—CH 2 CH 2 CH 2 —Si (OCH 3 3 ) A MEK solution containing 3 ⁇ was obtained.
  • Example 6 2-perfluorodecylethanol (Daikin Kogyo Co., Ltd.) 14.0 parts (26.9 mmol parts), 3- (triethoxysilyl) propyl isocyanate (Chisso Corporation) 6.65 parts (26.9 mmol parts) And 0.02 part of dilauric acid di-n-butyltin were dissolved in 170 parts of dehydrated MEK and then reacted at about 25 ° C.
  • Example 7 2- (perfluorobutyl) ethyl acrylate (Daikin Industries, Ltd.) 15.9 parts (50.0 mmol parts), 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) 9.80 parts ( 50.0 mmol parts) and 2,2′-azobisisobutyronitrile 410 ⁇ 10 ⁇ 3 parts (2.50 mmol parts) were dissolved in 231 parts of tetrahydrofuran (hereinafter abbreviated as THF).
  • THF tetrahydrofuran
  • Example 8 2-perfluorobutyl ethanol (Daikin Industries, Ltd.) 5.0 parts (18.9 mmol parts), 3- (triethoxysilyl) propyl isocyanate (Chisso Corporation) 4.68 parts (18.9 mmol parts) And 0.02 part of dilauric acid di-n-butyltin were dissolved in 87 parts of dehydrated MEK and reacted at about 25 ° C.
  • Example 9 (1) 2- (perfluorobutyl) ethyl acrylate (Daikin Industries, Ltd.) 23.3 parts (73.3 mmol), 2-mercaptoethanol (Nacalai Tesque) 6.00 parts (76.9 mmol) Part) and 2,2′-azobisisobutyronitrile 600 ⁇ 10 ⁇ 3 part (3.65 mmol part) were dissolved in 350 parts of toluene, and then heated under reflux for 24 hours under an argon atmosphere.
  • Example 10 4.0 parts (10.1 mmol parts) of the intermediate (9 ′) obtained in (1) of Example 9, 0.76 parts (10.6 mmol parts) of acrylic acid (Nacalai Tesque) and triphenyl
  • a THF solution prepared by dissolving 2.78 parts (10.6 mmol parts) of phosphine (Nacalai Tesque Corporation) in 30 parts of dehydrated THF 4.47 parts of a 40% toluene solution of azodiethylcarboxylic acid (Nacalai Tesque Corporation) ( 10.6 mmol part) was added dropwise under an argon atmosphere and ice cooling. After completion of the dropping, the temperature was returned to room temperature (about 25 ° C.), and the reaction was further continued for 24 hours.
  • Example 11 5.0 parts (13.6 mmol parts) of the intermediate (9 ′) obtained in (1) of Example 9, 1.28 parts (14.9 mmol parts) of methacrylic acid (Nacalai Tesque) and tri 6.65 parts of a 40% toluene solution of azodiethylcarboxylic acid (Nacalai Tesque) in a THF solution in which 3.91 parts (14.9 mmol) of phenylphosphine (Nacalai Tesque) is dissolved in 50 parts of dehydrated THF. (14.9 mmol) was added dropwise under an argon atmosphere and ice cooling. After completion of the dropping, the temperature was returned to room temperature (about 25 ° C.), and the reaction was further continued for 24 hours.
  • Example 15 > 1H, 1H, 2H, 2H-Nonafluoro-1-hexanol (Tokyo Chemical Industry Co., Ltd.) 5.24 parts (19.8 mmol parts), 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd.) 3.08 parts (19 0.8 mmol part) and 0.02 part di-n-butyltin dilaurate were dissolved in 72 parts dehydrated THF and reacted at about 25 ° C. for 24 hours under an argon atmosphere to obtain the polymerizable compound (15) of the present invention.
  • a THF solution containing C 4 F 9 —CH 2 CH 2 —OCONH—CH 2 CH 2 —OCOC (CH 3 ) ⁇ CH 2 was obtained.
  • Example 16 2- (perfluorobutyl) ethyl acrylate (Daikin Industries Co., Ltd.) 6.0 parts (18.9 mmol parts), triethoxysilane (Tokyo Chemical Industry Co., Ltd.) 3.09 parts (18.9 mmol parts) and the 0.1MTHF solution very small amount of potassium hexachloroplatinate (IV), was dissolved in THF81 parts, argon, by 24 hours at reflux, the polymerizable compound of the present invention (16); C 4 F 9 - A THF solution containing CH 2 CH 2 —OCO—CH 2 CH 2 —Si (OC 2 H 5 ) 3 ⁇ was obtained.
  • Example 17 (1) 2- (perfluorobutyl) ethyl acrylate (Daikin Industries, Ltd.) 12.5 parts (39.3 mmol), 2-mercaptoethylamine hydrochloride (Nacalai Tesque) 4.68 g (41.2) Mmol) and 2,2′-azobisisobutyronitrile (323 ⁇ 10 ⁇ 3 parts) (1.97 mmol parts) were dissolved in 125 parts of ethanol and then heated to reflux for 24 hours under an argon atmosphere. After completion of the reaction, ethanol was removed, 1N aqueous sodium hydroxide solution was added, and the mixture was extracted with toluene. 14.0 parts of liquid intermediate (17 ′); C 4 F 9 —CH 2 CH 2 —OCOCH 2 CH 2 —S—CH 2 CH 2 NH 2 by removing toluene after washing the toluene layer with water Obtained.
  • Example 19 4.0 parts (10.1 mmol parts) of the intermediate (17 ') obtained in Example 17 (1), 2.5 parts of 3- (triethoxysilyl) propyl isocyanate (Chisso Corporation) (10. 1 mmol part) and 0.02 part of di-n-butyltin dilaurate were dissolved in 59 parts of dehydrated MEK, and then reacted at about 25 ° C. for 24 hours under an argon atmosphere to obtain the polymerizable compound (19) of the present invention; An MEK solution containing C 4 F 9 —CH 2 CH 2 —OCOCH 2 CH 2 —S—CH 2 CH 2 NHCONH—CH 2 CH 2 CH 2 —Si (OCH 2 CH 3 ) 3 was obtained.
  • Example 20 (1) Perfluorobutyl iodide (Tokyo Chemical Industry Co., Ltd.) 16.9 parts (48.8 mmol parts), 2-mercaptoethanol (Nacalai Tesque Corporation) 3.8 parts (48.8 mmol parts) in DMF / Water (5: 1) dissolved in 60 ml, sodium formate (Nacalai Tesque) 3.3 parts (48.8 mmol), sodium sulfite heptahydrate (Nacalai Tesque) 12.3 g (48. 8 mmol) was added and stirred overnight at room temperature (about 25 ° C.). After completion of the reaction, extraction was performed with diethyl ether.
  • Tokyo Chemical Industry Co., Ltd. 16.9 parts (48.8 mmol parts), 2-mercaptoethanol (Nacalai Tesque Corporation) 3.8 parts (48.8 mmol parts) in DMF / Water (5: 1) dissolved in 60 ml, sodium formate (Nacalai Tesque) 3.3
  • Example 21 2.8 parts (9.4 mmol parts) of the intermediate (20 ′) obtained in Example 20 (1), 1.33 parts (9.4 mmol parts) of 2-acryloyloxyethyl isocyanate (Showa Denko KK) ) And 0.01 part of di-n-butyltin dilaurate are dissolved in 37 parts of dehydrated THF and then reacted at about 25 ° C. for 24 hours under an argon atmosphere to obtain the polymerizable compound (21) of the present invention; C 4 F A THF solution containing 9 -SCH 2 CH 2 —OCONH—CH 2 CH 2 —OCOCH ⁇ CH 2 was obtained.
  • Example 22 2.6 parts (8.8 mmol parts) of the intermediate (20 ′) obtained in (1) of Example 20 and 1.37 parts (8.8 mmol parts) of 2-methacryloyloxyethyl isocyanate (Showa Denko KK) ) And 0.01 part of di-n-butyltin dilaurate are dissolved in 36.5 parts of dehydrated THF, followed by reaction at about 25 ° C. for 24 hours under an argon atmosphere to obtain the polymerizable compound (22) of the present invention; C A THF solution containing 4 F 9 —SCH 2 CH 2 —OCONH—CH 2 CH 2 —OCOC (CH 3 ) ⁇ CH 2 was obtained.
  • Example 26 Intermediate (23 ′) 2.53 part (8.6 mmol part) obtained in (1) of Example 23, 0.77 part (8.9 mmol part) of methacrylic acid (Nacalai Tesque) and tri 3.90 parts of a 40% toluene solution of azodiethylcarboxylic acid (Nacalai Tesque Corporation) in a THF solution prepared by dissolving 2.36 parts (9.0 mmol parts) of phenylphosphine (Nacalai Tesque Corporation) in 50 parts of dehydrated THF. (9.0 mmol parts) was added dropwise under an argon atmosphere and ice cooling.
  • Example 27 (1) 2- (perfluorobutyl) ethyl acrylate (Daikin Industries, Ltd.) 12.5 parts (39.3 mmol), 1.2-aminoethanol (Nacalai Tesque) 1.2 parts (19.6 mmol) Part) was dissolved in 200 parts of toluene and heated under reflux for 24 hours under an argon atmosphere.
  • Example 28 (1) 5.5 parts (70.5 mmol) of 2-mercaptoethanol (Nacalai Tesque Co., Ltd.) is dissolved in 200 parts of dimethyl sulfoxide, and 4.8 parts of potassium hydroxide ⁇ Nacalai Tesque Co., Ltd. ⁇ (72. 9 mmol parts) of aqueous solution was added and stirred at room temperature (about 25 ° C.) until homogeneous. Then, 25.0 parts (66.8 mmol parts) of 2- (perfluorobutyl) ethyl iodide (Tokyo Chemical Industry Co., Ltd.) was added and stirred at room temperature (about 25 ° C.) for 1 day.
  • Example 31 (1) 9.8 parts (30.2 mmol part) of the intermediate (28 ′) obtained in (1) of Example 28 was dissolved in 200 ml of methylene chloride and cooled with ice water. 14.0 parts (81.1 mmol parts) of m-chloroperbenzoic acid (Nacalai Tesque Co., Ltd.) was added in portions at 10 ° C. or lower. After the addition, the temperature was returned to room temperature (about 25 ° C.) and reacted for 24 hours. After completion of the reaction, the mixture was washed with an aqueous sodium hydrogen carbonate solution, an aqueous sodium thiosulfate solution, and water, and then methylene chloride was removed. The obtained oil was recrystallized from hexane / ethyl acetate to obtain 8.7 parts of intermediate (31 ′); C 4 F 9 —CH 2 CH 2 —SO 2 —CH 2 CH 2 OH.
  • the intermediate member (31 ') is the chemical structure of, 1 H-NMR was confirmed by analysis ⁇ 4.16 (t, 2H, C 4 F 9 -CH 2 CH 2 -SO 2 -CH 2 C H 2 OH) , 3.39-3.44 (m, 2H, C 4 F 9 -CH 2 C H 2 -SO 2 -CH 2 CH 2 OH), 3.26 (t, 2H, C 4 F 9 -CH 2 CH 2 -SO 2 -C H 2 CH 2 OH), 2.60-2.79 (m, 2H, C 4 F 9 -C H 2 CH 2 -SO 2 -CH 2 CH 2 OH) ⁇ .
  • Example 32 Intermediate (31 ′) 2.1 parts (5.9 mmol parts) obtained in Example 31 (1), 2-acryloyloxyethyl isocyanate (Showa Denko KK) 0.83 parts (5.9 mmol parts) ) And 0.01 part of di-n-butyltin dilaurate were dissolved in 40 parts of dehydrated THF, reacted at about 25 ° C. for 24 hours under an argon atmosphere, then THF was removed and recrystallized from hexane / ethyl acetate. As a result, 2.6 parts of the polymerizable compound (32) of the present invention; C 4 F 9 —CH 2 CH 2 —SO 2 —CH 2 CH 2 OCONH—CH 2 CH 2 —OCOCH ⁇ CH 2 was obtained.
  • Example 33 2.41 parts (6.8 mmol parts) of the intermediate (31 ′) obtained in Example 31 (1), 1.68 parts (6. 6 parts) of 3- (triethoxysilyl) propyl isocyanate (Chisso Corporation) 8 mmol parts) and 0.01 parts of di-n-butyltin dilaurate were dissolved in 37 parts of dehydrated THF and then reacted at about 25 ° C. for 24 hours under an argon atmosphere to obtain the polymerizable compound (33) of the present invention; A THF solution containing C 4 F 9 —CH 2 CH 2 —SO 2 —CH 2 CH 2 OCONH—CH 2 CH 2 CH 2 —Si (OCH 2 CH 3 ) 3 was obtained.
  • Example 34 Intermediate (27 ') 3.1 parts (4.4 mmol parts) obtained in Example 27 (1), 2-acryloyloxyethyl isocyanate (Showa Denko KK) 0.62 parts (4.4 mmol parts) ) And 0.01 part of di-n-butyltin dilaurate are dissolved in 33 parts of dehydrated THF and then reacted at about 25 ° C. for 24 hours under an argon atmosphere to obtain the polymerizable compound (34) of the present invention; (C 4 F 9 —CH 2 CH 2 —OCO—CH 2 CH 2 ) 2 N—CH 2 CH 2 OCONH—CH 2 CH 2 —OCOCH ⁇ CH 2 was obtained.
  • Example 36 (1) 4.5 parts (39.6 mmol parts) of 2-mercaptoethylamine hydrochloride (Nacalai Tesque Co., Ltd.) is dissolved in 140 parts of dimethyl sulfoxide, and sodium bicarbonate ⁇ Nacalai Tesque Co., Ltd. ⁇ 6.6 parts ( 78.6 mmol parts) was added and stirred to achieve uniform dispersion. Then, 14.7 parts (39.3 mmol parts) of 2- (perfluorobutyl) ethyl iodide (Tokyo Chemical Industry Co., Ltd.) was added and stirred at room temperature (about 25 ° C.) for 3 days.
  • 2-mercaptoethylamine hydrochloride Nacalai Tesque Co., Ltd.
  • sodium bicarbonate ⁇ Nacalai Tesque Co., Ltd. ⁇ 6.6 parts ( 78.6 mmol parts) was added and stirred to achieve uniform dispersion.
  • Example 37 The polymerizable compound (36) of the present invention, which was isolated by obtaining the same procedure as in Example 36 (2), ⁇ C 4 F 9 -CH 2 CH 2 -S-CH 2 CH 2 -NHCONH-CH 2 CH 2- OCOC (CH 3 ) ⁇ CH 2 ⁇ 5.0 parts (10.4 mmol part) was dissolved in 75 ml of methylene chloride and cooled with ice water. 4.9 parts (28.4 mmol parts) of m-chloroperbenzoic acid (Nacalai Tesque Co., Ltd.) was added in portions at 10 ° C. or lower, and then returned to room temperature (about 25 ° C.) and reacted for 24 hours.
  • m-chloroperbenzoic acid Nacalai Tesque Co., Ltd.
  • Example 38 1.68 parts (10.0 mmol parts) of 2H-hexafluoro-2-propanol (Nacalai Tesque), 2.47 parts (10.0 mmol) of 3- (triethoxysilyl) propyl isocyanate (Chiso Corporation) Part) and 0.02 part of di-n-butyltin dilaurate were dissolved in 38 parts of dehydrated THF, and then reacted at about 25 ° C. for 24 hours under an argon atmosphere, whereby the polymerizable compound (38) of the present invention; A THF solution containing CF 3 ) 2 CH—OCONH—CH 2 CH 2 CH 2 —Si (OCH 2 CH 3 ) 3 was obtained.
  • Example 39 2H-hexafluoro-2-propanol (Nacalai Tesque) 2.0 parts (11.9 mmol), 2-methacryloyloxyethyl isocyanate (Showa Denko) 1.84 parts (11.9 mmol) and After dissolving 0.02 part of di-n-butyltin dilaurate in 35 parts of dehydrated THF, it is reacted at about 25 ° C. for 24 hours under an argon atmosphere to obtain the polymerizable compound (39) of the present invention; (CF 3 ) 2 A THF solution containing CH—OCONH—CH 2 CH 2 —OCOC (CH 3 ) ⁇ CH 2 was obtained.
  • m-chloroperbenzoic acid Nacalai Tesque Co., Ltd.
  • m-chloroperbenzoic acid Nacalai Tesque Co., Ltd.
  • Example 43 (1) Intermediate (20 ′) obtained by the same procedure as in Example 20 (1); C 4 F 9 —S—CH 2 CH 2 OH, 8.90 parts (30.0 mmol) was salified It was dissolved in 210 ml of methylene and cooled with ice water. After adding 4.1 parts (82.0 mmol parts) of m-chloroperbenzoic acid (Nacalai Tesque Co., Ltd.) at 10 ° C. or less, the mixture was returned to room temperature (about 25 ° C.) and reacted for 24 hours.
  • m-chloroperbenzoic acid Nacalai Tesque Co., Ltd.
  • Example 44 Intermediate (43 ′) 2.04 parts (6.2 mmol parts) obtained in Example 43 (1), 3- (triethoxysilyl) propyl isocyanate (Chisso Corporation) 1.54 parts (6. 2 mmol parts) and 0.01 parts of di-n-butyltin dilaurate were dissolved in 32 parts of dehydrated THF, and then reacted at about 25 ° C. for 24 hours under an argon atmosphere to obtain the polymerizable compound (44) of the present invention; A THF solution containing C 4 F 9 —SO 2 —CH 2 CH 2 OCONH—CH 2 CH 2 CH 2 —Si (OCH 2 CH 3 ) 3 was obtained.
  • Example 45 (1) 18.4 parts (109.5 mmol parts) of 2H-hexafluoro-2-propanol (Nacalai Tesque Corporation) are dissolved in 100 ml of ethyl alcohol, and 7.6 parts of potassium hydroxide (Nacalai Tesque Corporation) (115 .3 mmol part) was added and stirred until homogeneous. Subsequently, 15.0 parts (120.0 mmol parts) of 2-bromoethanol (Nacalai Tesque Co., Ltd.) was added and heated to reflux overnight. After most of the ethanol was removed, water was added and extracted with diethyl ether. After the ether layer was washed with water, the ether was removed to obtain 10.2 parts of intermediate (45 ′); (CF 3 ) 2 CH—OCH 2 CH 2 —OH.
  • Example 47 (1) 1H-1- (trifluoromethyl) trifluoroethyl acrylate (Daikin Industries, Ltd.) 10.0 parts (45.0 mmol parts), 2-mercaptoethanol (Nacalai Tesque Corporation) 3.7 parts (47 .4 mmol part) and 2,2′-azobisisobutyronitrile 370 ⁇ 10 ⁇ 3 parts (2.25 mmol part) were dissolved in 200 parts of toluene, and then heated under reflux for 24 hours under an argon atmosphere.
  • 1H-1- (trifluoromethyl) trifluoroethyl acrylate 10.0 parts (45.0 mmol parts), 2-mercaptoethanol (Nacalai Tesque Corporation) 3.7 parts (47 .4 mmol part) and 2,2′-azobisisobutyronitrile 370 ⁇ 10 ⁇ 3 parts (2.25 mmol part) were dissolved in 200 parts of toluene, and then heated under reflux for 24 hours under an argon atmosphere.
  • intermediate (47 ′) was confirmed by 1 H-NMR analysis ⁇ 5.50-5.57 (m, 1H, (CF 3 ) 2 —C H —OCOCH 2 CH 2 —), 3.33 (t, 2H, -S-CH 2 C H 2 OH), 2.83 (t, 2H, -OCOCH 2 C H 2 -S-CH 2 CH 2 OH) 2.51-2.65 (m, 4H , —OCOC H 2 CH 2 —S—C H 2 CH 2 OH) ⁇ .
  • Example 48 12.5 parts (74.4 mmol parts) of 2H-hexafluoro-2-propanol (Nacalai Tesque) are dissolved in 100 ml of ethyl alcohol, and 4.9 parts (74.4 mmol) of potassium hydroxide (Nacalai Tesque). Part) was added and stirred until uniform. Next, 9.1 parts (60.0 mmol parts) of p-chloromethylstyrene (Seimi Chemical Co., Ltd.) was added and heated to reflux overnight. After most of the ethanol was removed, water was added and extracted with diethyl ether.
  • Example 50 1.4 parts (3.0 mmol parts) of the polymerizable compound (49) of the present invention obtained in Example 49, 0.6 parts of 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) (3 0.02 mmol part) and 2,2′-azobisisobutyronitrile 25 ⁇ 10 ⁇ 3 parts (0.15 mmol part) were dissolved in 18 parts of methyl alcohol and then at reflux temperature in an argon atmosphere for 24 hours.
  • Example 51 (1) 6.5 parts (51.6 mmol parts) of 4-hydroxythiophenol (Nacalai Tesque Corporation) was dissolved in 50 parts of dimethyl sulfoxide, and 5.2 parts of sodium hydrogen carbonate (Nacalai Tesque Corporation) (61 9 mmol parts), and then 19.3 parts (51.6 mmol parts) of 2- (perfluorobutyl) ethyl iodide (Tokyo Chemical Industry Co., Ltd.) was added and stirred at room temperature (about 25 ° C.) for 1 day. did. After completion of the reaction, water was added and extracted with toluene.
  • intermediate (51 ′) was confirmed by 1 H-NMR analysis ⁇ 7.34, 6.81 (d, 4H, C 4 F 9 —CH 2 CH 2 —S—C 6 H 4 —OH) , 2.96-3.02 (m, 2H, C 4 F 9 -CH 2 C H 2 -S-C 6 H 4 -OH), 2.22-2.42 (m, 2H, C 4 F 9 -C H 2 CH 2 -S-C 6 H 4 -OH) ⁇ .
  • Example 52 2.5 parts (5.1 mmol parts) of the polymerizable compound (51) of the present invention obtained in Example 51, 1.0 part (5) of 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) .1 mmol part) and 2,2′-azobisisobutyronitrile 42 ⁇ 10 ⁇ 3 parts (0.25 mmol part) were dissolved in 32 parts of methyl alcohol and then at reflux temperature for 24 hours under an argon atmosphere.
  • Example 53 (1) 200 parts of water was added to 25.0 parts (200.0 mmol parts) of 4-aminothiophenol (Nacalai Tesque Corporation), and 22.9 parts (220.0 mmol) of 35% hydrochloric acid (Nacalai Tesque Corporation). Part) was added to obtain a uniform solution. Water of the obtained solution was removed, washed with ethanol and dried to obtain 27.6 parts of white solid 4-aminothiophenol hydrochloride.
  • Example 55 (1) 10.0 parts (69.4 mmol) of 4-hydroxybutyl acrylate (Tokyo Chemical Industry Co., Ltd.) and 11.0 parts (139.2 mmol) of dehydrated pyridine (Nacalai Tesque) 100 ml of dehydrated THF Dissolved in 13.5 parts (72.5 mmol) of 4- (chloromethyl) benzoyl chloride (Tokyo Chemical Industry Co., Ltd.) at 10 ° C. or less. After completion of the dropwise addition, the temperature was returned to room temperature (about 25 ° C.) and stirred as it was for 24 hours. After completion of the reaction, the reaction mixture was poured into ice water and extracted with hexane.
  • Example 56 The intermediate (51 ′) 3.10 parts (8.3 mmol parts) obtained in Example 51 (1) was dissolved in 50 parts of dimethyl sulfoxide, and 0.4 parts of sodium hydroxide (Nacalai Tesque Co., Ltd.) was added. Dissolved water (4 parts) was added and stirred at room temperature (about 25 ° C.) until homogeneous. Subsequently, 2.47 parts (8.3 mmol part) of the intermediate (55 ′) obtained in Example 55 (1) was added and stirred at room temperature (about 25 ° C.) for 1 day.
  • sodium hydroxide Nacalai Tesque Co., Ltd.
  • Example 57 (1) 4.23 parts (26.2 mmol) of 4-aminothiophenol hydrochloride obtained in (1) of Example 53 was dissolved in 50 parts of dimethyl sulfoxide, and sodium hydrogen carbonate (Nacalai Tesque) 2.6 parts (31.0 mmol part) was added and stirred to achieve uniform dispersion. Then, 9.8 parts (26.2 mmol parts) of 2- (perfluorobutyl) ethyl iodide (Tokyo Chemical Industry Co., Ltd.) was added and stirred at room temperature (about 25 ° C.) for 3 days. After completion of the reaction, water was added and extracted with hexane.
  • Example 58 The polymerizable compound (57) of the present invention isolated after being obtained by the same operation as in Example 57 (2) ⁇ C 4 F 9 —CH 2 CH 2 —S—C 6 H 4 —NHCONH—CH 2 CH 2- OCOC (CH 3 ) ⁇ CH 2 ⁇ 3.2 parts (10.4 mmol parts) was dissolved in 75 ml of methylene chloride and cooled with ice water. 4.9 parts (28.4 mmol parts) of m-chloroperbenzoic acid (Nacalai Tesque Co., Ltd.) was added in portions at 10 ° C. or lower, and then returned to room temperature (about 25 ° C.) and reacted for 24 hours.
  • m-chloroperbenzoic acid Nacalai Tesque Co., Ltd.
  • Example 60 The polymerizable compound (59) of the present invention obtained in Example 59 ⁇ C 4 F 9 —S—C 6 H 4 —NHCOCH ⁇ CH 2 ⁇ 1.1 parts (2.8 mmol part) was dissolved in 50 ml of methylene chloride. And cooled with ice water. After adding 1.4 parts (8.1 mmol parts) of m-chloroperbenzoic acid (Nacalai Tesque Co., Ltd.) at 10 ° C. or lower, the mixture was returned to room temperature (about 25 ° C.) and reacted for 24 hours.
  • m-chloroperbenzoic acid Nacalai Tesque Co., Ltd.
  • m-chloroperbenzoic acid Nacalai Tesque
  • Example 62 4.0 parts (6.7 mmol parts) of the polymerizable compound (55) obtained by the same method as in Example 55 (2) was dissolved in 100 ml of methylene chloride and cooled with ice water. After adding 3.5 parts (20.3 mmol parts) of m-chloroperbenzoic acid (Nacalai Tesque, Inc.) at 10 ° C. or less, the mixture was returned to room temperature (about 25 ° C.) and reacted for 24 hours. After completion of the reaction, the mixture was washed with an aqueous sodium hydrogen carbonate solution, an aqueous sodium thiosulfate solution, and water, and then methylene chloride was removed.
  • m-chloroperbenzoic acid Nacalai Tesque, Inc.
  • Example 63> (1) 3.4 parts (10 mmol parts) of the intermediate (49 ′) obtained in (1) of Example 49 were dissolved in 70 ml of methylene chloride and cooled with ice water. After 4.7 parts (27.3 mmol parts) of m-chloroperbenzoic acid (Nacalai Tesque Co., Ltd.) was added in portions at 10 ° C. or lower, the mixture was returned to room temperature (about 25 ° C.) and reacted for 24 hours. After completion of the reaction, the mixture was washed with an aqueous sodium hydrogen carbonate solution, an aqueous sodium thiosulfate solution, and water, and then methylene chloride was removed. The obtained oil was recrystallized from hexane / ethyl acetate to obtain 2.4 parts of an intermediate compound (63 ′); C 4 F 9 —SO 2 —C 6 H 4 —OH.
  • Example 64 3.7 parts (10 mmol parts) of the intermediate (51 ′) obtained in Example 51 (1) was dissolved in 70 ml of methylene chloride and cooled with ice water. After charging 4.7 parts (27.3 mmol parts) of m-chloroperbenzoic acid (Nacalai Tesque Co., Ltd.) at 10 ° C. or lower, the mixture was returned to room temperature (about 25 ° C.) and reacted for 24 hours. . After completion of the reaction, the mixture was washed with an aqueous sodium hydrogen carbonate solution, an aqueous sodium thiosulfate solution, and water, and then methylene chloride was removed.
  • m-chloroperbenzoic acid Nacalai Tesque Co., Ltd.
  • reaction solution is poured into water, and the resulting precipitate is filtered and dried, and recrystallized with toluene, whereby the polymerizable compound (64) of the present invention; C 4 F 9 —CH 2 CH 2 —SO 2 —C 6 0.9 part of H 4 —OCH 2 —C 6 H 4 —CH ⁇ CH 2 was obtained.
  • Example 65 Intermediate (63 ′) obtained by the same operation as in Example 63 (1); 1.9 parts (5.0 mmol parts) of C 4 F 9 —SO 2 —C 6 H 4 —OH, methacrylic acid ( To a THF solution in which 0.6 part (7.0 mmol part) of Nacalai Tesque Corporation and 1.45 part (5.5 mmol part) of triphenylphosphine (Nacalai Tesque Corporation) was dissolved in 30 parts of dehydrated THF, azo 2.4 parts (5.5 mmol parts) of a 40% toluene solution of diethylcarboxylic acid (Nacalai Tesque, Inc.) was added dropwise under an argon atmosphere and ice cooling.
  • Example 66 Polymerizable compound (48) of the present invention obtained in the same manner as in Example 48; p- (CF 3 ) 2 CH—OCH 2 C 6 H 4 —CH ⁇ CH 2 3.4 parts (12.0 mmol part) ), 2.3 parts (12.0 mmol parts) of 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) and 99 ⁇ 10 ⁇ 3 parts of 2,2′-azobisisobutyronitrile (0 .61 mmol part) was dissolved in 52 parts of methyl alcohol and then reacted at reflux temperature for 24 hours under an argon atmosphere to obtain a polymerizable compound (66) of the present invention; p- (CF 3 ) 2 CH—OCH 2 A methyl alcohol solution containing C 6 H 4 —CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3 ) 3 was obtained.
  • Example 67 Polymerizable compound (63) of the present invention obtained in the same manner as in Example 63; C 4 F 9 —SO 2 —C 6 H 4 —OCH 2 —C 6 H 4 —CH ⁇ CH 2 0.6 part ( 1.2 mmol part), 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) 0.23 part (1.2 mmol part) and 2,2′-azobisisobutyronitrile 10 ⁇ 10 -3 parts (0.06 mmol part) was dissolved in 25 parts of methyl alcohol and then reacted at reflux temperature for 24 hours under an argon atmosphere to obtain the polymerizable compound (67) of the present invention; C 4 F 9 -SO to obtain a methyl alcohol solution containing 2 -C 6 H 4 -OCH 2 -C 6 H 4 -CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3.
  • Example 68 Polymerizable compound (64) of the present invention obtained in the same manner as in Example 64; C 4 F 9 —CH 2 CH 2 —SO 2 —C 6 H 4 —OCH 2 —C 6 H 4 —CH ⁇ CH 2 1.9 parts (3.6 mmol parts), 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) 0.7 parts (3.6 mmol parts) and 2,2′-azobisisobuty 30 ⁇ 10 ⁇ 3 parts (0.18 mmol part) of nitrile are dissolved in 25 parts of ethyl alcohol and then reacted for 24 hours at reflux temperature in an argon atmosphere to obtain the polymerizable compound (68) of the present invention; C 4 F 9-methyl alcohol solution containing -CH 2 CH 2 -SO 2 -C 6 H 4 -OCH 2 -C 6 H 4 -CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3.
  • m-chloroperbenzoic acid Nacalai Tesque Co., Ltd.
  • the chemical structure of the polymerizable compound (70) of the present invention was confirmed by 1 H-NMR analysis ⁇ 7.24, 6.41 (d, 4H, —S—C 6 H 4 —), 3.83 (q , 6H, OC H 2 CH 3 ), 3.62 (t, 2H, —C 6 H 4 —OC H 2 CH 2 CH 2 ), 1.83-1.94 (m, 2H, —C 6 H 4 -OCH 2 C H 2 CH 2) , 1.14 (t, 9H, OCH 2 C H 3), 0.70-0.76 (m, 2H, -C 6 H 4 -OCH 2 CH 2 C H 2 Si (OCH 2 CH 3) 3 ⁇ .
  • the surface of the slide glass when the polymerizable group is a trialkoxysilyl group or a monomethyl dialkoxy group
  • the surface of cotton the polymerizable group
  • Modified (meth) acryloxy group or (meth) acryloylamino group) was measured.
  • the mixture was stirred for 2 days to prepare a treatment liquid (surface treatment agent).
  • Slide glass ⁇ 76 mm, 26 mm, 1.2 mm; immersed in 2-propanol saturated solution of sodium hydroxide for 17 hours, washed with water and dried (60 ° C., 2 hours) ⁇ into the treatment liquid (surface treatment agent) After dipping and taking out the slide glass, the liquid was drained and heat-treated at 130 ° C. for 10 minutes to obtain a surface-modified slide glass.
  • the contact angle (degree) was similarly measured about the surface of the glass slide which is not surface-modified, and these average values were shown as Table 1 in Table 1.
  • the contact angle (degree) was similarly measured about the surface of the cotton cloth which is not surface-modified, and these average values were shown in Table 1 as the blank 2.
  • the value in parentheses is a value when a treatment liquid (polymerization liquid) prepared by adding 0.5 g of tetraethoxysilane to the above-described polymerizable compound when the polymerizable group is a trialkoxysilyl group,
  • a treatment liquid (polymerization) prepared by adding 20 mol% of methyl methacrylate to the polymerizable compound to the above-described polymerizable compound. This is the value when using (Liquid).
  • the polymerizable compound of the present invention could be obtained ⁇ simply in a short time ⁇ more easily than the polymerizable compound of the comparative example. That is, in order to obtain the polymerizable compound of the comparative example, four reaction steps are required, and furthermore, it is necessary to use sodium borohydride, phosphorus tribromide, and trimethoxysilane that are water-inhibiting, toxic, and corrosive. there were. On the other hand, the polymerizable compound of the present invention can be produced by two or less reaction steps, can be easily obtained from the market, and can use a relatively stable and low-toxic raw material. Further, when the polymerizable compound of the present invention was used, the contact angle was equal to or greater than that when the polymerizable compound of the comparative example was used.
  • Example 71 After uniformly mixing 15 parts of MEK solution containing the polymerizable compound (1) obtained in Example 1, 30 parts of ethanol, 0.5 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, the mixture was heated at about 25 ° C.
  • the surface treatment agent (1) of the present invention was prepared by stirring for 2 days.
  • Example 72 After uniformly mixing 10 parts of the MEK solution containing the polymerizable compound (1) obtained in Example 1 and 20 parts of silica sol (Colcoat N-103X; Colcoat Co., Ltd.), the mixture was stirred at about 25 ° C. for 2 days. A surface treatment agent (2) was prepared.
  • Example 73 After uniformly mixing 15 parts of MEK solution containing the polymerizable compound (2) obtained in Example 2, 30 parts of ethanol, 0.5 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, the mixture was heated at about 25 ° C.
  • the surface treatment agent (3) of the present invention was prepared by stirring for 2 days.
  • Example 74 After uniformly mixing 10 parts of the MEK solution containing the polymerizable compound (2) obtained in Example 2 and 20 parts of silica sol (Colcoat N-103X; Colcoat Co., Ltd.), the mixture was stirred at about 25 ° C. for 2 days. A surface treatment agent (4) was prepared.
  • Example 75 After uniformly mixing 15 parts of MEK solution containing the polymerizable compound (3) obtained in Example 3, 30 parts of ethanol, 0.5 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, the mixture was heated at about 25 ° C.
  • the surface treatment agent (5) of the present invention was prepared by stirring for 2 days.
  • Example 76 After uniformly mixing 10 parts of the MEK solution containing the polymerizable compound (3) obtained in Example 3 and 20 parts of silica sol (Colcoat N-103X; Colcoat Co., Ltd.), the mixture was stirred at about 25 ° C. for 2 days. A surface treatment agent (6) was prepared.
  • Example 77 After uniformly mixing 15 parts of MEK solution containing the polymerizable compound (4) obtained in Example 4, 30 parts of ethanol, 0.3 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, the mixture was heated at about 25 ° C.
  • the surface treatment agent (7) of the present invention was prepared by stirring for 2 days.
  • Example 78 After uniformly mixing 10 parts of the MEK solution containing the polymerizable compound (6) obtained in Example 6 and 10 parts of silica sol (Colcoat N-103X; Colcoat Co., Ltd.), the mixture was stirred at about 25 ° C. for 2 days. A surface treatment agent (8) was prepared.
  • the contact angle was equivalent to that when only the polymerizable compound of the present invention was used.

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Abstract

La présente invention concerne un composé polymérisable pouvant être obtenu au moyen d'un procédé plus simple. Le composé polymérisable est représenté par la formule (1) ou (2). [Rf-{R1-X0-(CO)t-R2-}q]mX1-R3-Z (1) Rf-R1-X2-CO(NH)r-R3-Z (2) Dans ces formules, Rf représente un polyfluoroalkyle qui peut contenir une liaison éther; R1 représente une liaison directe, un alkylène ou un arylène; R2 représente une liaison directe, un alkylène ou un arylène; R3 représente une liaison directe, une liaison uréthane, un alkylène qui peut contenir une liaison urée ou un arylène; X0 et X2 représentent chacun une liaison directe ou un groupe représenté par -O-, -S- ou -NH-; X1 représente une liaison directe ou un groupe représenté par -S-, -SO2-, -O-, -NH- ou >N-; Z représente un groupe polymérisable sélectionné parmi trialkoxysilyle, monométhyldialkoxysilyle, trihalogénosilyle, (méth)acryloxy, (méth)acryloylamino, vinyle ou 1-méthylvinyle; q, t et r représentent chacun 0 ou 1; et m représente 1 ou 2.
PCT/JP2009/000095 2008-01-11 2009-01-13 Composé polymérisable et procédé de production de ce dernier WO2009087981A1 (fr)

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CN102643303A (zh) * 2012-04-13 2012-08-22 阜新恒通氟化学有限公司 一种含氟抗指纹剂的制备方法
JP2013515067A (ja) * 2009-12-22 2013-05-02 スリーエム イノベイティブ プロパティズ カンパニー フッ素化アリーレン含有化合物、方法、及びそれから調製されるポリマー
JP2014144935A (ja) * 2013-01-30 2014-08-14 Tosoh F-Tech Inc ペンタエリスリトール骨格を有する新規フッ素含有アルコキシシラン化合物、それを用いた表面改質剤およびその中間体
JP2014237576A (ja) * 2013-05-08 2014-12-18 株式会社Kri 修飾金属酸化物ナノ粒子
JP2015224187A (ja) * 2014-05-26 2015-12-14 ユニマテック株式会社 含フッ素ウレタン（メタ）アクリレートの製造法
WO2015194555A1 (fr) * 2014-06-17 2015-12-23 日産化学工業株式会社 Composition filmogène de sous-couche de résist contenant du silicium ayant un chromophore contenant un groupe phényle
JP2016179982A (ja) * 2011-08-10 2016-10-13 日産化学工業株式会社 スルホン構造を有する新規シラン化合物
CN106699939A (zh) * 2016-12-29 2017-05-24 中科院广州化学有限公司南雄材料生产基地 一种端氨基含氟丙烯酸酯预聚物及其制备方法
WO2017119371A1 (fr) 2016-01-08 2017-07-13 東ソー・エフテック株式会社 Nouveau composé fluoré possédant une liaison insaturée, et modificateur de surface mettant en œuvre celui-ci
KR101922256B1 (ko) 2011-04-12 2018-11-26 신에쓰 가가꾸 고교 가부시끼가이샤 플루오로알킬기를 갖는 알콕시실란 화합물 및 그의 제조 방법
CN110981756A (zh) * 2019-11-25 2020-04-10 三明学院 一种六氟异丙基丙烯酸酯类单体及其制备方法
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JP2011505422A (ja) * 2007-12-04 2011-02-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フルオロアルキルシラン
US20110143622A1 (en) * 2009-12-16 2011-06-16 E.I. Dupont De Nemours And Company Fluorinated acrylate compositions
JP2013515067A (ja) * 2009-12-22 2013-05-02 スリーエム イノベイティブ プロパティズ カンパニー フッ素化アリーレン含有化合物、方法、及びそれから調製されるポリマー
JP2011246422A (ja) * 2010-05-31 2011-12-08 Asahi Kasei E-Materials Corp フルオロアルカン誘導体、ゲル化剤及びゲル状組成物
CN102918131B (zh) * 2010-06-04 2015-08-19 旭硝子株式会社 拒水拒油剂和拒水拒油剂组合物
WO2011152498A1 (fr) * 2010-06-04 2011-12-08 旭硝子株式会社 Agent conférant hydrophobicité et oléophobicité, et composition d'agent conférant hydrophobicité et oléophobicité
CN102918131A (zh) * 2010-06-04 2013-02-06 旭硝子株式会社 拒水拒油剂和拒水拒油剂组合物
US8754183B2 (en) 2010-06-04 2014-06-17 Asahi Glass Company, Limited Water/oil repellent agent and water/oil repellent composition
JP5846118B2 (ja) * 2010-06-04 2016-01-20 旭硝子株式会社 撥水撥油剤および撥水撥油剤組成物
KR101922256B1 (ko) 2011-04-12 2018-11-26 신에쓰 가가꾸 고교 가부시끼가이샤 플루오로알킬기를 갖는 알콕시실란 화합물 및 그의 제조 방법
JP2016179982A (ja) * 2011-08-10 2016-10-13 日産化学工業株式会社 スルホン構造を有する新規シラン化合物
CN102643303A (zh) * 2012-04-13 2012-08-22 阜新恒通氟化学有限公司 一种含氟抗指纹剂的制备方法
JP2014144935A (ja) * 2013-01-30 2014-08-14 Tosoh F-Tech Inc ペンタエリスリトール骨格を有する新規フッ素含有アルコキシシラン化合物、それを用いた表面改質剤およびその中間体
JP2014237576A (ja) * 2013-05-08 2014-12-18 株式会社Kri 修飾金属酸化物ナノ粒子
JP2015224187A (ja) * 2014-05-26 2015-12-14 ユニマテック株式会社 含フッ素ウレタン（メタ）アクリレートの製造法
JP2019135238A (ja) * 2014-06-17 2019-08-15 日産化学株式会社 フェニル基含有クロモファーを有するシラン化合物
US11175583B2 (en) 2014-06-17 2021-11-16 Nissan Chemical Industries, Ltd. Silicon-containing resist underlayer film-forming composition having phenyl group-containing chromophore
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WO2015194555A1 (fr) * 2014-06-17 2015-12-23 日産化学工業株式会社 Composition filmogène de sous-couche de résist contenant du silicium ayant un chromophore contenant un groupe phényle
JPWO2015194555A1 (ja) * 2014-06-17 2017-04-20 日産化学工業株式会社 フェニル基含有クロモファーを有するシリコン含有レジスト下層膜形成組成物
US10197917B2 (en) 2014-06-17 2019-02-05 Nissan Chemical Industries, Ltd. Silicon-containing resists underlayer film-forming composition having phenyl group-containing chromophore
WO2017119371A1 (fr) 2016-01-08 2017-07-13 東ソー・エフテック株式会社 Nouveau composé fluoré possédant une liaison insaturée, et modificateur de surface mettant en œuvre celui-ci
US11352457B2 (en) 2016-01-08 2022-06-07 Tosoh Finechem Corporation Fluorine-containing compound having unsaturated bond, and surface modifier using the same
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CN106699939B (zh) * 2016-12-29 2019-02-01 中科院广州化学有限公司南雄材料生产基地 一种端氨基含氟丙烯酸酯预聚物及其制备方法
JP2020097542A (ja) * 2018-12-18 2020-06-25 Ａｇｃセイミケミカル株式会社 アルコキシシリル基含有フッ素化合物の製造方法、表面処理組成物の製造方法、および表面処理された部材の製造方法
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