WO2018216404A1 - 含フッ素コーティング剤組成物及び該組成物を含有する表面処理剤並びに物品 - Google Patents
含フッ素コーティング剤組成物及び該組成物を含有する表面処理剤並びに物品 Download PDFInfo
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- WO2018216404A1 WO2018216404A1 PCT/JP2018/016116 JP2018016116W WO2018216404A1 WO 2018216404 A1 WO2018216404 A1 WO 2018216404A1 JP 2018016116 W JP2018016116 W JP 2018016116W WO 2018216404 A1 WO2018216404 A1 WO 2018216404A1
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- 0 CC(C)(*=C)N=O Chemical compound CC(C)(*=C)N=O 0.000 description 5
- PBLVLXGAPMEPKW-UHFFFAOYSA-N CC(C)(NC)OC Chemical compound CC(C)(NC)OC PBLVLXGAPMEPKW-UHFFFAOYSA-N 0.000 description 1
- ZCPYNOKKGVIBMV-UHFFFAOYSA-N CC(N(C)c1cc(S)ccc1)=O Chemical compound CC(N(C)c1cc(S)ccc1)=O ZCPYNOKKGVIBMV-UHFFFAOYSA-N 0.000 description 1
- LMTGCJANOQOGPI-UHFFFAOYSA-N CC(N(C)c1ccccc1)=O Chemical compound CC(N(C)c1ccccc1)=O LMTGCJANOQOGPI-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N CN(C)c1ccccc1 Chemical compound CN(C)c1ccccc1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- 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
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
Definitions
- the present invention relates to a fluorine-containing coating agent composition, and more specifically, a hydroxyl group or hydrolyzable group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer residue and / or a partial (hydrolyzed) condensate thereof.
- the present invention relates to a fluorine-containing coating agent composition that forms a film excellent in water and oil repellency and abrasion resistance, a surface treatment agent containing the composition, and an article surface-treated with the surface treatment agent.
- 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.
- Patent Documents 1 to 6 JP-T 2008-534696, JP-T 2008-537557, JP 2012-072272 A, JP 2012-157856 A, JP 2013-136833 A, JP 2015-199906 A).
- the present invention has been made in view of the above circumstances, and includes a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof that can form a cured film having excellent water and oil repellency and abrasion resistance. It is an object of the present invention to provide a fluorine-containing coating agent composition containing the composition, a surface treatment agent containing the composition, and an article surface-treated with the surface treatment agent.
- a partial (hydrolyzed) condensate thereof a hydroxyl group or hydrolyzable group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer residue represented by the following general formula (1) and / or
- the present invention provides the following fluorine-containing coating agent composition, a surface treatment agent containing the composition, and an article surface-treated with the surface treatment agent.
- a fluorine-containing coating agent composition a surface treatment agent containing the composition
- an article surface-treated with the surface treatment agent [1] (A) a hydroxyl group or hydrolyzable group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer residue and / or a partial (hydrolyzed) condensate thereof; and (B) a fluorooxyalkylene group-containing polymer residue.
- It contains an organosilicon compound containing a modified hydroxyl group or hydrolyzable group and a polyether group and / or a partial (hydrolyzed) condensate thereof, and the mixing mass ratio of the component (A) to the component (B) is 15 : 85 to 85:15 (provided that the total of component (A) and component (B) is 100).
- (A) component is the following general formula (1) (Wherein Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, A is independently a divalent to 7valent organic group, and R is independently an alkyl group having 1 to 4 carbon atoms or A phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, m is an integer of 1 to 6, and ⁇ is 1 or 2.) A hydroxyl group or hydrolyzable group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer residue represented by: and / or a partial (hydrolyzed) condensate thereof, (B) component is the following general formula (2) or (3) Rf- [N (V) ⁇ (E) ⁇ ] ⁇ (2) (Wherein Rf and ⁇ are the same as above, N is an oxygen atom, a silicon atom or a nitrogen atom which may independently contain a tri to o
- W may be a hydrogen atom or the following formula (4a)
- Y ′ is a divalent to hexavalent hydrocarbon group which may have a silicon atom and / or a siloxane bond, and R is independently an alkyl group having 1 to 4 carbon atoms.
- R is independently an alkyl group having 1 to 4 carbon atoms.
- X is independently a hydroxyl group or a hydrolyzable group
- n is an integer of 1 to 3
- a is an integer of 1 to 5
- b is an integer of 1 to 5, Is 1 or 2.
- a 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond
- B 1 is independently an oxygen atom, a diorganosilylene group or a diorganosiloxane structure.
- It is an alkylene group having 1 to 5 carbon atoms which may contain one or more selected, and Rf, X, R, n and ⁇ are the same as above.
- B) component is the following general formula (6) Wherein Rf, Y, X, R, n and ⁇ are the same as above, Z is independently a single bond, a siloxane bond or a silylene group, and L is independently an alkylene group having 1 to 4 carbon atoms.
- each repeating unit may be linear or branched, and each repeating unit is randomly And d is an integer of 0 to 3, and the unit may be linear or branched.
- ⁇ is 2
- the Rf group is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (8) [2] Or the fluorine-containing coating agent composition as described in [3].
- each repeating unit may be linear or branched, and each repeating unit is randomly And each d is independently an integer of 0 to 3, and the unit may be linear or branched.
- Y is an alkylene group having 3 to 10 carbon atoms, an alkylene group having 2 to 8 carbon atoms including an arylene group having 6 to 8 carbon atoms, and an alkylene having 2 to 8 carbon atoms.
- the fluorine-containing coating agent composition according to any one of [3] to [5].
- Y ′ is an alkylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 8 carbon atoms including an arylene group having 6 to 8 carbon atoms, or 2 to 6 carbon atoms including a diorganosilylene group.
- An alkylene group having 2 to 6 carbon atoms containing 10 straight chain divalent organopolysiloxane residues, and a straight chain having 2 to 10 silicon atoms or a branched chain having 3 to 10 silicon atoms, or [3] to [6] are groups selected from the group consisting of divalent to tetravalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a cyclic divalent to tetravalent organopolysiloxane residue.
- Z is a single bond, a straight chain having 2 to 10 silicon atoms, a branched or cyclic divalent to tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, and
- X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, carbon
- the fluorine-containing coating agent composition according to any one of [2] to [8], which is selected from the group consisting of alkenyloxy groups having 2 to 10 and halogen groups.
- the hydrolyzable group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer residue represented by the formula (1) is represented by any of the following formulas: [2] to [9] The fluorine-containing coating agent composition in any one.
- the fluorine-containing coating agent composition of the present invention comprises a polymer having a fluoropolyether group containing a hydroxyl group or a hydrolyzable group, and a polymer having a fluoropolyether group containing a hydroxyl group or a hydrolyzable group and a polyether group.
- the hydroxyl group or hydrolyzable group part strengthens the adhesion to the substrate, and the polyether group part improves the substrate adhesion and wettability.
- Articles surface-treated with a surface treatment containing a fluorine-containing coating composition containing a partial (hydrolyzed) condensate are excellent in water and oil repellency, as well as steel wool wear resistance and erase rubber wear resistance. It is excellent.
- the fluorine-containing coating agent composition of the present invention comprises (A) a hydroxyl group or hydrolyzable group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer residue and / or a partial (hydrolyzed) condensate thereof; B) a hydroxyl group or hydrolyzable group modified with a fluorooxyalkylene group-containing polymer residue and an organosilicon compound containing a polyether group and / or a partial (hydrolyzed) condensate thereof; (B) A fluorine-containing coating agent composition having a mixing mass ratio ((A) :( B)) of 15:85 to 85:15, preferably the mixing mass ratio of 30:70 to 90: 10 and particularly preferably 40:60 to 80:20 (provided that the sum of component (A) and component (B) is 100).
- Thing is. If there are too many components (A) or too little component (B), good steel wool durability cannot be obtained, and if there are too few components (A) or too much component (B), good eraser durability can be obtained. Therefore, a fluorine-containing coating composition having a mixing mass ratio outside the above range cannot achieve both good steel wool durability and eraser durability.
- the fluorine-containing coating agent composition of the present invention is obtained by mixing the component (A) and the component (B) at a specific ratio, thereby improving substrate adhesion and wettability, and having excellent water and oil repellency, It has excellent steel wool wear resistance and erase rubber wear resistance.
- Component (A) is a hydroxyl group or hydrolyzable group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer residue and / or a partial (hydrolyzed) condensate thereof (that is, the organosilicon compound) (Organosiloxane oligomer having 2 or more, preferably 3 or more residual hydroxyl groups or hydrolyzable groups in the molecule), preferably formed by partial (hydrolysis) condensation of The hydroxyl group or hydrolyzable group-containing organosilicon compound modified with the fluorooxyalkylene group-containing polymer residue represented by (1) and / or a partial (hydrolyzed) condensate thereof.
- organosilicon compound Organic siloxane oligomer having 2 or more, preferably 3 or more residual hydroxyl groups or hydrolyzable groups in the molecule
- Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue
- A is independently a divalent to 7valent organic group
- R is independently an alkyl group having 1 to 4 carbon atoms or A phenyl group
- X is independently a hydroxyl group or a hydrolyzable group
- n is an integer of 1 to 3
- m is an integer of 1 to 6, and ⁇ is 1 or 2.
- Rf, R, X, n and ⁇ are the same as described above.
- Y is independently a divalent to hexavalent hydrocarbon group which may have a silicon atom and / or a siloxane bond.
- Y ′ is a divalent to hexavalent hydrocarbon group and may have a silicon atom and / or a siloxane bond.
- a 1 is a divalent hydrocarbon group such as an alkylene group having 2 to 6 carbon atoms which may contain an ether bond
- B 1 is independently an oxygen atom, diorganosilylene group
- This is an alkylene group having 1 to 5 carbon atoms which may contain one or more selected from an organosiloxane structure
- Rf, X, R, n and ⁇ are the same as above.
- Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue
- ⁇ is 1 (that is, Rf is a monovalent fluorooxyalkylene) In the case of a group-containing polymer residue)
- It is preferably a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (7), and when ⁇ is 2 (that is, Rf is divalent fluorooxy) In the case of an alkylene group-containing polymer residue)
- each repeating unit may be linear or branched, and each repeating unit is randomly And each d is independently an integer of 0 to 3, and the unit may be linear or branched.
- D is an integer of 0 to 3 independently for each unit, preferably 1 or 2, and the unit may be linear or branched.
- Rf include the following. (Wherein 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, v is an integer of 1 to 24. Each repeating unit may be bonded at random.)
- A is a divalent to 7-valent, preferably a 2- to 5-valent organic group, and specific examples thereof include the following.
- Y is a divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent hydrocarbon group, which may have a silicon atom and / or a siloxane bond.
- Y 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 having 2 to 8 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene / arylene group having 8 to 16 carbon atoms), or an alkylene group having 2 to 8 carbon atoms is a silyl having 1 to 4 carbon atoms.
- Examples thereof include a divalent to hexavalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a hexavalent organopolysiloxane residue, preferably an alkylene group having 3 to 10 carbon atoms, phenyl An alkylene group having 2 to 6 carbon atoms, and an alkylene group having 2 to 4 carbon atoms bonded to each other via a silalkylene structure having 1 to 4 carbon atoms or a silarylene structure having 6 to 10 carbon atoms 2 Alkylene having 2 to 10 carbon atoms in a bond of a divalent group, a linear or cyclic 2 to 10 silicon atom, or a branched or cyclic divalent or
- R 1 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 an aryl group having 6 to 10 carbon atoms such as a phenyl group
- 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.
- Examples of the linear, branched or cyclic divalent to hexavalent organopolysiloxane residues having 2 to 10, preferably 2 to 5 silicon atoms include the following. (Wherein 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 an integer of 0 to 8) And preferably 0 or 1, h + j is an integer of 3 to 10, preferably 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3.)
- Y include the following groups.
- W is a hydrogen atom or a group represented by the following formula (4a).
- R, X and n are the same as above.
- Y ′ is a divalent to hexavalent hydrocarbon group which may have a silicon atom and / or a siloxane bond.
- Y ′ is a divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent hydrocarbon group, which may have a silicon atom and / or a siloxane bond.
- Y ′ include ethylene groups, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), hexamethylene groups and other alkylene groups having 2 to 10 carbon atoms, phenylene A C 2-8 alkylene group including a C 6-8 arylene group such as a group (for example, a C 8-16 alkylene / arylene group, etc.), a diorganosilylene group such as a dimethylsilylene group or a diethylsilylene group.
- a divalent group having 2 to 6 carbon atoms preferably an alkylene group having 3 to 10 carbon atoms, an alkylene group having 2 to 6 carbon atoms including a phenylene group, or 2 to 6 carbon atoms including a dimethylsilylene group.
- An alkylene group having 2 to 4 carbon atoms a divalent group in which the alkylene groups having 2 to 4 carbon atoms are bonded to each other via a silalkylene structure having 1 to 4 carbon atoms or a silarylene structure having 6 to 10 carbon atoms,
- a divalent to tetravalent radical which is an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a siloxane residue, more preferably an alkylene group having 3 to 6 carbon atoms.
- silalkylene structure the silarylene structure, and the linear, branched, or cyclic divalent to hexavalent organopolysiloxane residue having 2 to 10, preferably 2 to 5 silicon atoms are described above. The thing similar to what was done can be illustrated.
- Y ′ include the following groups.
- a 1 is a divalent hydrocarbon group such as an alkylene group having 2 to 6 carbon atoms which may contain an ether bond, and specific examples thereof include the following groups.
- B 1 may independently contain one or more selected from a diorganosilylene group such as an oxygen atom, a dimethylsilylene group and a diorganosiloxane structure such as dimethylsiloxane.
- a diorganosilylene group such as an oxygen atom
- a dimethylsilylene group such as a dimethylsilylene group
- a diorganosiloxane structure such as dimethylsiloxane.
- An alkylene group having 1 to 5 carbon atoms, and specific examples thereof include the following groups.
- R represents an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group or a butyl group, or a phenyl group.
- X is a hydroxyl group or a hydrolyzable group.
- Examples of such X include an alkoxy group having 1 to 10 carbon atoms such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, an alkoxyalkoxy group having 2 to 10 carbon atoms such as a methoxymethoxy group and a methoxyethoxy group, Examples thereof include an acyloxy group having 1 to 10 carbon atoms such as an acetoxy group and an alkenyloxy group having 2 to 10 carbon atoms such as an isopropenoxy group. Of these, a methoxy group and an ethoxy group are preferable.
- n is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
- m is an integer of 1 to 6, preferably an integer of 1 to 4, a is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1.
- ⁇ is 1 or 2.
- Examples of the structure of the hydrolyzable group-containing organosilicon compound modified with the fluorooxyalkylene group-containing polymer residue represented by the formula (1) include the following structures. (In the formula, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1 + q1 is an integer of 10 to 105. Each unit shown in parentheses may be bonded at random.)
- the hydroxyl group or hydrolyzable group-containing organosilicon compound modified with the fluorooxyalkylene group-containing polymer residue represented by the formula (4) is disclosed in JP-A-2015-199906 and JP-A-2016-204656.
- the hydroxyl group- or hydrolyzable-group-containing organosilicon compound modified with the fluorooxyalkylene group-containing polymer residue represented by the formula (5) can be produced by the method described in International Application No. PCT / It can be produced by the method described in JP2016-080666.
- Component (B) is an organosilicon compound containing a hydroxyl group or hydrolyzable group and a polyether group modified with a fluorooxyalkylene group-containing polymer residue and / or a partial (hydrolyzed) condensate thereof.
- N is an oxygen atom, a silicon atom or a nitrogen atom which may independently contain a tri to octavalent organic group which may be substituted with fluorine
- V is independently a monovalent group having a hydroxyl group or a hydrolyzable group at the terminal
- E is a monovalent group independently having an oxyalkylene group
- ⁇ is an integer of 1 to 6
- ⁇ is 1 to 6
- ⁇ + ⁇ is an integer of 2 to 7.
- G and E ′ are linearly connected, and G and E ′ are randomly selected. May be arranged.
- (A) component does not contain an unsubstituted polyether group other than a fluoropolyether group (fluorooxyalkylene group) in the compound
- (B) component contains a fluoropolyether group in the compound.
- it has a polyether group (that is, an unsubstituted polyether group), and the component (A) and the component (B) are different in this respect.
- Rf and ⁇ may be the same as those exemplified for Rf and ⁇ in the above formula (1).
- N may contain an oxygen atom, a silicon atom or a nitrogen atom, and may be a fluorine-substituted tri to octavalent organic group
- the tri to octavalent organic group may be Is-(J) t -M (-) w (wherein J is a divalent organic group, M is a trivalent or tetravalent group having a carbon atom and / or a silicon atom, and 3 to 8)
- w is an integer of 2 to 7, preferably an integer of 2 to 5. There is no limit.
- J is a divalent organic group, and is a linking group between the Rf group and the M group.
- a group represented by-(f is an integer of 2 to 4), or one or more structures selected from the group consisting of diorganosiloxane groups, which may contain an unsubstituted or substituted carbon group having 2 to 12 carbon atoms
- a divalent organic group preferably an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms, which may contain the above structure.
- the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group) ),
- An alkylene group such as a hexamethylene group or an octamethylene group, an arylene group such as a phenylene group, or a combination of two or more of these groups (an alkylene / arylene group, etc.), and the hydrogen of these groups.
- Examples thereof include those in which part or all of the atoms are substituted with halogen atoms such as fluorine.
- unsubstituted or substituted alkylene groups having 2 to 4 carbon atoms and phenylene groups are preferable.
- J examples include the following groups. (In the formula, f and c are integers of 2 to 4, g ′ and h ′ are integers of 1 to 4, and e is an integer of 1 to 50.)
- M is a group selected from a trivalent or tetravalent group having a carbon atom and / or a silicon atom, and a tri to octavalent siloxane residue.
- -TC [T is preferably independently An alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, a hydroxyl group, or K 3 SiO— (K is independently a hydrogen atom, preferably an alkyl group having 1 to 3 carbon atoms, or an aryl group such as a phenyl group)
- a trivalent group represented by -TSi (T is the same as above)
- a group selected from a tetravalent group represented by C ⁇ , a tetravalent group represented by —Si ⁇ , and a tri- to octavalent siloxane residue and
- the organopolysiloxane residue may have 1 to 8 carbon atoms, more preferably 1 to 4 alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, or phenyl group.
- the alkylene group in the silalkylene bond has 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
- Examples of such M include those shown below.
- V is independently a monovalent group having a hydroxyl group or a hydrolyzable group at the terminal, and is preferably a monovalent organic group in which a plurality of hydroxyl groups or hydrolyzable groups are introduced.
- V include groups represented by the following formulas (9a) to (9f). Wherein R and X are the same as above, X 1 is a hydrolyzable group, a ′ is 2 or 3, y is an integer of 0 to 10, and z is independently 1 to 10 D is a single bond or a divalent organic group optionally substituted with fluorine having 1 to 20 carbon atoms, b ′ is an integer of 2 to 6, and e is an integer of 1 to 50. is there.)
- X 1 is a hydrolyzable group, and examples thereof are the same as the hydrolyzable group of X. Of these, a methoxy group and an ethoxy group are preferable.
- X 1 is preferably bonded to the M (terminal) silicon atom and has a structure of ⁇ Si—X 1 .
- D is a single bond or a divalent organic group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, which may be substituted with fluorine, preferably a divalent hydrocarbon group.
- a divalent hydrocarbon group alkylene such as methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group, etc.
- D is preferably an ethylene group, a propylene group, or a phenylene group.
- y is an integer of 0 to 10, preferably 2 to 8
- z is an integer of 1 to 10, preferably 2 to 8
- b ′ is It is an integer of 2 to 6, preferably an integer of 2 to 4, and e is an integer of 1 to 50, preferably an integer of 1 to 10.
- E is independently a monovalent group having an oxyalkylene group, and can be represented by —Z ′ (— (LO) 1 —R) f ′ , where Z ′ is an oxygen atom, or A divalent or trivalent group which is a combination of X ′ and an oxygen atom, and X ′ is a C 2-20 divalent which may have a silicon atom, a siloxane bond, a silalkylene bond or a silarylene bond. Alternatively, it is a trivalent group and may have a hydroxyl group or a hydrolyzable group on the silicon atom.
- Z ′ examples include —O—, —O—X′—O—, —X′—O—, —X ′ (— O—) 2 and the like, and among these, an oxygen atom (—O—) is preferable.
- L is independently an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, or a butylene group, and the carbon number may be single or mixed.
- l is an integer of 1 to 20, preferably an integer of 1 to 10.
- R is the same as the above, 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 preferred.
- f ′ is 1 or 2.
- Examples of such E include the following groups.
- ⁇ is an integer of 1 to 6, preferably 1 or 2
- ⁇ is an integer of 1 to 6, preferably 1 or 2
- ⁇ + ⁇ is an integer of 2 to 7, preferably 2 or 3.
- Q is independently a single bond or a divalent organic group, and is a linking group between the Rf group and the G group or E ′ group.
- divalent organic group an amide bond, an ether bond, an ester bond, a diorganosilylene group such as a dimethylsilylene group, —Si [—OH] [— (CH 2 ) f —Si (CH 3 ) 3 ] — (F is an integer of 2 to 4), 1 or 2 or more types of structures selected from the group consisting of diorganosiloxane groups, unsubstituted or substituted 2 having 2 to 12 carbon atoms
- a valent organic group preferably an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms, which may contain the above structure.
- the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group) ),
- An alkylene group such as a hexamethylene group or an octamethylene group, an arylene group such as a phenylene group, or a combination of two or more of these groups (an alkylene / arylene group, etc.), and the hydrogen of these groups.
- Examples thereof include those in which part or all of the atoms are substituted with halogen atoms such as fluorine.
- unsubstituted or substituted alkylene groups having 2 to 4 carbon atoms and phenylene groups are preferable.
- Examples of such a divalent organic group of Q include the following groups. (In the formula, f is an integer of 2 to 4, c is an integer of 2 to 4, and e is an integer of 1 to 50.)
- G is independently a divalent group having a hydroxyl group or a hydrolyzable group, and specific examples thereof include the following groups. (Wherein X is the same as above, d ′ is an integer of 0 to 10, preferably 1 to 8, and e ′ is an integer of 2 to 10, preferably 3 to 8.) )
- E ′ is a divalent group having an oxyalkylene group independently, and may have a hydroxyl group or a hydrolyzable group. Specific examples include the following groups. (In the formula, X, L, l, R, d ′, and e ′ are the same as above.)
- B is independently a hydrogen atom, an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group or a butyl group, or a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. It is a halogen atom.
- ⁇ is an integer of 0 to 10, preferably an integer of 1 to 4.
- E ′ has a hydroxyl group or a hydrolyzable group.
- ⁇ is an integer of 1 to 10, preferably an integer of 1 to 4.
- said G and E ' are connected with linear form, These G and E' may be arranged at random, respectively.
- Examples of the structure of the fluoropolyether group-containing polymer containing a hydrolyzable group and a polyether group represented by the above formulas (2) and (3) include the following structures. By changing the combination of Rf, N, V, E, Q, G, E ′, and B in the above formulas (2) and (3), fluoropolymer containing several hydrolyzable groups and polyether groups An ether group-containing polymer is obtained.
- 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
- r1 is an integer of 1 to 100
- s1 is an integer of 1 to 100
- p1 + q1 + r1 + s1 is 12
- it is an integer of ⁇ 199
- preferred values of p1 + q1 and p1 + q1 + r1 + s1 of the respective formulas are shown in parentheses.
- ⁇ 1 (that is, Rf is a monovalent fluorooxyalkylene group-containing polymer residue) or ⁇ is 2 (that is, Rf is a divalent fluorooxyalkylene group-containing polymer represented by the above formula (2))
- Examples of the method for preparing an organosilicon compound containing a hydrolyzable group and a polyether group modified with a fluorooxyalkylene group-containing polymer residue in the case of a residue include the following methods.
- Fluoropolyether group-containing polymer having at least one polyether group and olefin moiety at one end of molecular chain or both ends of molecular chain is dissolved in a solvent such as fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene.
- an organosilicon compound having a SiH group and a hydrolyzable terminal group (such as a halogen atom or an alkoxy group) is mixed in a molecule such as trichlorosilane or trialkoxysilane, and a hydrosilylation reaction catalyst such as chloroplatinic acid / vinyl Aging in a toluene solution of a siloxane complex at a temperature of 40 to 120 ° 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. .
- a halogenated (organic) silicon compound containing SiH group such as trichlorosilane is used as the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule
- a substituent (halogen) on the silyl group is then used.
- Atom may be converted into an alkoxy group such as a methoxy group as another hydrolyzable group.
- fluoropolyether group-containing polymer having one or more polyether groups and olefin moieties at one end of the molecular chain or both ends of the molecular chain include the following. (Wherein l is the same as above, 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, and r1 is an integer of 1 to 100. In parentheses Each unit shown may be randomly combined.)
- a fluoropolyether group-containing polymer having one or more polyether groups and olefin moieties at one end of the molecular chain or both ends of the molecular chain for example, a hydroxyl group at one end of the molecular chain or both ends of the molecular chain
- Hydrofluoropolyether group-containing polymer having at least one olefin moiety and a polyether group introducing agent a hydroxyl group of a fluoropolyether group-containing polymer having at least one hydroxyl group and one olefin moiety at one end of the molecular chain or both ends of the molecular chain 1 to 15 equivalents, more preferably 1.5 to 9 equivalents, and even more preferably 2 to 7 equivalents of a polyether group introducing agent with respect to 1 equivalent, and an additive that improves the reactivity if necessary in the presence of a base Or a solvent at a temperature of 0 to 90 ° C., preferably 50 to 80
- a fluoropolyether group-containing polymer having one or more polyether groups and olefin moieties at one end of molecular chain or both ends of molecular chain for example, a hydroxyl group at one end of molecular chain or both ends of molecular chain
- a fluoropolyether group-containing polymer having at least one olefin moiety and an organosilicon compound having no hydrolyzable end groups in the molecule and having at least two SiH groups, 7 organosilicon compounds having no hydrolyzable end groups in the molecule and two or more SiH groups for one equivalent of hydroxyl group of a fluoropolyether group-containing polymer having one or more hydroxyl groups and olefin moieties at the ends
- To 30 equivalents more preferably 5 to 20 equivalents, still more preferably about 10 equivalents, preferably in the presence of a dehydrogenation catalyst at 0 to 60 ° C.
- a fluoropolyether group-containing polymer having at least one SiH group and at least one olefin moiety at both chain ends is obtained.
- a fluoropolyether group-containing polymer having one or more SiH groups and one or more olefin moieties at one end of the molecular chain or both ends of the molecular chain and a polyether compound having an olefin moiety in the molecule (for example, alkenyl at one end of the molecular chain) Oxy-group-blocked polyalkylene oxide compound, etc.) in the molecule with respect to 1 equivalent of SiH group of a fluoropolyether group-containing polymer having one or more SiH groups and one or more olefin sites at one end of the molecular chain or at both ends of the molecular chain.
- a hydrosilylation reaction catalyst for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex, 0 ⁇ 120 ° C., preferably 60 ⁇ 100 ° C., more preferably at a temperature of about 80 ° C., 1 ⁇ 72 hours, preferably 20-36 hours, more preferably be aged for about 24 hours.
- a fluoropolyether group-containing polymer having one or more polyether groups and olefin moieties at one end of the molecular chain or both ends of the molecular chain for example, an olefin at one end of the molecular chain or both ends of the molecular chain.
- a fluoropolyether group-containing polymer having three sites is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene, and first has a SiH group and a polyoxyalkylene group in the molecule.
- an SiH group and a polyoxyalkylene group are contained in the molecule with respect to 1 equivalent of a reactive end group of a fluoropolyether group-containing polymer having three olefin moieties at one end of the molecular chain or both ends of the molecular chain.
- a hydrosilylation reaction catalyst such as a chloroplatinic acid / vinylsiloxane complex in a toluene solution is present at 40 to 120 ° C., preferably 60 to 100 ° C. C., more preferably about 80.degree. C., for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours.
- organosilicon compound having a SiH group and a hydrolyzable end group in the molecule examples include the following. Trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silanes or siloxanes Compounds and the like.
- the amount of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule is the olefin of the fluoropolyether group-containing polymer having at least one polyether group and olefin moiety at one end of the molecular chain or both ends of the molecular chain. It can be used so as to be 1 to 4 equivalents, more preferably 1.5 to 3 equivalents, and still more preferably 2 to 2.5 equivalents with respect to 1 equivalent of the site.
- a substituent (halogen) on the silyl group is then used.
- Atom may be converted into an alkoxy group such as a methoxy group as another hydrolyzable group, and used when converting a substituent (halogen atom) on the silyl group into another hydrolyzable group.
- the reagent that can be used include alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol.
- the amount used is an addition reaction product 100 of a fluoropolyether group-containing polymer having one or more polyether groups and one or more olefinic sites at one molecular chain terminal or both molecular chain terminals and a SiH group-containing halogenated (organic) silicon compound. 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and still more preferably 65 parts by mass can be used with respect to parts by mass.
- the solvent examples include a fluorine-based solvent.
- the fluorine-based solvent 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-3-methoxy-2- (trifluoromethyl) pentane and other hydrofluoroether (HFE) solvents (trade name: Novec series, manufactured by 3M) ), A perfluoro solvent composed of a fully fluorinated compound (trade name: Fluorinert series, manufactured by 3M), and the like.
- HFE hydrofluoroether
- the amount of the solvent used is 10 to 300 parts by weight, preferably 50 to 100 parts by weight with respect to 100 parts by weight of the fluoropolyether group-containing polymer having one or more polyether groups and olefin moieties at one end of the molecular chain or both ends of the molecular chain.
- 150 parts by mass, more preferably about 100 parts by mass can be used.
- hydrosilylation reaction catalyst examples include the following. Platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxane, acetylene alcohols, etc., tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium Platinum group metal catalysts such as Preferred are platinum compounds such as vinylsiloxane coordination compounds.
- the amount of hydrosilylation reaction catalyst used is 0 in terms of transition metal (mass) relative to the mass of the fluoropolyether group-containing polymer having one or more polyether groups and olefin moieties at one end of the molecular chain or at both ends of the molecular chain. Used in an amount of 1 to 100 ppm, more preferably 1 to 50 ppm.
- ⁇ is 1 (that is, Rf is a monovalent fluorooxyalkylene group-containing polymer residue) or ⁇ is 2 (that is, Rf is a divalent fluorooxyalkylene group represented by the above formula (2).
- Rf is a monovalent fluorooxyalkylene group-containing polymer residue
- ⁇ is 2
- Rf is a divalent fluorooxyalkylene group represented by the above formula (2).
- a fluoropolyether group-containing polymer having at least one olefin moiety at one end of the molecular chain or at both ends of the molecular chain is dissolved in a solvent, for example, a fluorinated solvent such as 1,3-bis (trifluoromethyl) benzene, to obtain trichlorosilane
- a solvent for example, a fluorinated solvent such as 1,3-bis (trifluoromethyl) benzene
- hydrosilylation reaction catalyst for example, 40 to 40
- fluoropolyether group-containing polymer having one or more olefinic sites at one end of the molecular chain or at both ends of the molecular chain include the following. (Wherein p1 and q1 are the same as above. Each unit shown in parentheses may be bonded at random)
- SiH group-containing halogenated (organic) silicon compound having a SiH group and a hydrolyzable end group in the molecule examples include trichlorosilane, tribromosilane, triiodosilane, and the like.
- Use amount of SiH group-containing halogenated (organic) silicon compound having SiH group and hydrolyzable end group in the molecule includes fluoropolyether group having one or more olefinic sites at one end of molecular chain or both ends of molecular chain It can be used so that it is 1 to 4 equivalents, more preferably 1.5 to 2.5 equivalents, and still more preferably about 2 equivalents per 1 equivalent of the olefin moiety of the polymer.
- polyether alcohols that can be used when converting a substituent (halogen atom) on a silyl group into a polyether group include, for example, a polysiloxane having one end of a molecular chain blocked with a hydroxyl group and the other end blocked with a methoxy group.
- examples thereof include polyether alcohols such as ethylene oxide. (Wherein l is the same as above)
- polyether alcohol examples include NOOX UNIOX M-200, UNIOX M-300, UNIOX M-400, and the like manufactured by NOF Corporation.
- the amount used is a fluoropolyether group-containing polymer having one or more olefinic sites at one end of the molecular chain or both ends of the molecular chain and a SiH group-containing halogenated (organic) silicon having a SiH group and a hydrolyzable end group in the molecule. 5 to 100 parts by mass, more preferably 20 to 50 parts by mass, and still more preferably 35 parts by mass can be used with respect to 100 parts by mass of the addition reaction product with the compound.
- Examples of a reagent that can be used when converting a substituent (halogen atom) on the silyl group into another hydrolyzable group include alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol. Can be mentioned.
- the amount used is a fluoropolyether group-containing polymer having one or more olefinic sites at one end of the molecular chain or both ends of the molecular chain and a SiH group-containing halogenated (organic) silicon having a SiH group and a hydrolyzable end group in the molecule. 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and still more preferably 65 parts by mass can be used with respect to 100 parts by mass of the addition reaction product with the compound.
- the solvent examples include a fluorine-based solvent.
- the fluorine-based solvent 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-3-methoxy-2- (trifluoromethyl) pentane and other hydrofluoroether (HFE) solvents (trade name: Novec series, manufactured by 3M) ), A perfluoro solvent composed of a fully fluorinated compound (trade name: Fluorinert series, manufactured by 3M), and the like.
- HFE hydrofluoroether
- the amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, with respect to 100 parts by mass of the fluoropolyether group-containing polymer having one or more olefin sites at one end of the molecular chain or both ends of the molecular chain. More preferably, about 100 parts by mass can be used.
- hydrosilylation reaction catalyst examples include the following. Platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxane, acetylene alcohols, etc., tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium Platinum group metal catalysts such as Preferred are platinum compounds such as vinylsiloxane coordination compounds.
- the amount of the hydrosilylation reaction catalyst used is 0.1 to 100 ppm in terms of transition metal (mass) with respect to the mass of the fluoropolyether group-containing polymer having one or more olefin sites at one molecular chain end or both molecular chain ends. More preferably, it is used in an amount of 1 to 50 ppm.
- ⁇ is 1 (that is, Rf is a monovalent fluorooxyalkylene group-containing polymer residue) or ⁇ is 2 (that is, Rf is a divalent fluorooxyalkylene group represented by the above formula (2).
- the following method may be used. Can be mentioned.
- a fluoropolyether group-containing polymer having two or more olefin moieties at one molecular chain end or both molecular chain ends is dissolved in a solvent, for example, a fluorinated solvent such as 1,3-bis (trifluoromethyl) benzene,
- a fluorinated solvent such as 1,3-bis (trifluoromethyl) benzene
- An organosilicon compound having a SiH group and a polyoxyalkylene group in the molecule is mixed, and a part of the olefin moiety of the fluoropolyether group-containing polymer is reacted with the SiH group of the polyoxyalkylene group and SiH group-containing organosilicon compound.
- a hydrosilylation reaction catalyst for example, a toluene solution of chloroplatinic acid / vinylsiloxane complex
- a temperature of 40 to 120 ° C. preferably 60 to 100 ° C., more preferably about 80 ° C., preferably 1 to 72 hours, preferably Aging is carried out for 20 to 36 hours, more preferably about 24 hours.
- an organosilicon compound having a SiH group and a hydrolyzable terminal group (alkoxy group or the like) in a molecule such as trimethoxysilane is mixed, and the remaining olefin part of the fluoropolyether group-containing polymer and the SiH of the organosilicon compound are mixed.
- a hydrosilylation reaction catalyst such as chloroplatinic acid / vinylsiloxane complex in a toluene solution is present at a temperature of 40 to 120 ° C., preferably 60 to 100 ° C., more preferably about 80 ° C. Aging is performed for 72 hours, preferably 20 to 36 hours, more preferably about 24 hours.
- a halogenated (organic) silicon compound containing SiH group such as trichlorosilane is used as the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule
- a substituent (halogen) on the silyl group is then used.
- Atom may be converted into an alkoxy group such as a methoxy group as another hydrolyzable group.
- fluoropolyether group-containing polymer having two or more olefin moieties at one molecular chain terminal or both molecular chain terminals include the following. (Wherein p1 and q1 are the same as above. Each unit shown in parentheses may be bonded at random)
- organosilicon compound having a SiH group and a polyoxyalkylene group in the molecule examples include the following. (Wherein l is the same as above)
- the amount of the organosilicon compound having a SiH group and a polyoxyalkylene group in the molecule is based on 1 equivalent of an olefin moiety of a fluoropolyether group-containing polymer having two or more olefin moieties at one molecular chain terminal or both molecular chain terminals. And 0.1 to 0.9 equivalents, more preferably 0.3 to 0.7 equivalents, and even more preferably about 0.5 equivalents.
- organosilicon compound having a SiH group and a hydrolyzable end group in the molecule examples include the following. Trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silanes or siloxanes Compounds and the like.
- the amount of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule is equivalent to 1 equivalent of an olefin moiety of a fluoropolyether group-containing polymer having two or more olefin moieties at one molecular chain end or both molecular chain ends.
- it can be used in an amount of 0.1 to 0.9 equivalent, more preferably 0.3 to 0.7 equivalent, still more preferably about 0.5 equivalent.
- the solvent examples include a fluorine-based solvent.
- the fluorine-based solvent 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-3-methoxy-2- (trifluoromethyl) pentane and other hydrofluoroether (HFE) solvents (trade name: Novec series, manufactured by 3M) ), A perfluoro solvent composed of a fully fluorinated compound (trade name: Fluorinert series, manufactured by 3M), and the like.
- HFE hydrofluoroether
- the amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, with respect to 100 parts by mass of the fluoropolyether group-containing polymer having two or more olefin moieties at one molecular chain end or both molecular chain ends. More preferably, about 100 parts by mass can be used.
- hydrosilylation reaction catalyst examples include the following. Platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxane, acetylene alcohols, etc., tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium Platinum group metal catalysts such as Preferred are platinum compounds such as vinylsiloxane coordination compounds.
- the amount of the hydrosilylation reaction catalyst used is 0.1 to 100 ppm in terms of transition metal (mass) with respect to the mass of the fluoropolyether group-containing polymer having two or more olefin moieties at one molecular chain end or both molecular chain ends. More preferably, it is used in an amount of 1 to 50 ppm.
- ⁇ 1 (that is, Rf is a monovalent fluorooxyalkylene group-containing polymer residue) or ⁇ is 2 (that is, Rf is a divalent fluorooxyalkylene group-containing polymer represented by the above formula (3)
- Examples of the method for preparing an organosilicon compound containing a hydrolyzable group and a polyether group modified with a fluorooxyalkylene group-containing polymer residue in the case of a residue include the following methods.
- a fluoropolyether group-containing polymer having iodine at one end of the molecular chain or both ends of the molecular chain is dissolved in a solvent, for example, a fluorinated solvent such as 1,3-bis (trifluoromethyl) benzene, and di-t-butyl peroxide is obtained.
- a radical initiator such as vinyltrichlorosilane and vinyltrialkoxysilane
- an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule and a polyether compound having an olefin moiety in the molecule Add and mix.
- the molecular chain is aged by aging at a temperature of 60 to 180 ° C., preferably 90 to 150 ° C., more preferably about 120 ° C. for 1 to 20 hours, preferably 2 to 10 hours, more preferably about 6 hours.
- a temperature of 60 to 180 ° C. preferably 90 to 150 ° C., more preferably about 120 ° C. for 1 to 20 hours, preferably 2 to 10 hours, more preferably about 6 hours.
- an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule and a poly having an olefin moiety in the molecule Telomerization with ether compounds.
- the organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule and the polyether compound having an olefin moiety in the molecule may be added simultaneously, or after reacting either one first, The other may be reacted.
- numerator may have a hydroxyl group or a hydrolysable group, and when it has a hydroxyl group or a hydrolyzable group, an olefin site
- a reducing agent such as metallic zinc.
- an olefin-containing halogenated organosilicon compound such as vinyltrichlorosilane is used as the organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule
- a substituent on the silyl group (halogen atom) is then used. May be converted into an alkoxy group such as a methoxy group as another hydrolyzable group.
- fluoropolyether group-containing polymer having iodine at one end of the molecular chain or both ends of the molecular chain examples include the following. (Wherein 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, and r1 is an integer of 1 to 100. Each unit shown in parentheses is bonded randomly. May be.)
- organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule examples include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltriisopropeno Xysilane, vinyltriacetoxysilane, vinyltrichlorosilane, vinyltribromosilane, vinyltriiodosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, allyltriisopropoxysilane, allyltributoxysilane, allyltri Examples include isopropenoxysilane, allyltriacetoxysilane, allyltrichlorosilane, allyltribromosilane, allyltriiodosilane, and the following silanes.
- the amount used when using an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule is 1 equivalent of a reactive end group of a fluoropolyether group-containing polymer having iodine at one end of the molecular chain or both ends of the molecular chain 1 to 10 equivalents, more preferably 1.5 to 3 equivalents, and still more preferably about 2 equivalents.
- the polyether compound having an olefin moiety in the molecule may have a hydroxyl group or a hydrolyzable group.
- one end of a molecular chain shown below is blocked with an allyloxy group and the other end is blocked with a methoxy group.
- a molecular chain fragment terminal alkenyloxy group-blocked polyalkylene oxide compound such as polyethylene oxide, a silane compound having a terminal alkenyl group and a terminal polyether group, and the like. (Wherein d ′ and l are the same as above)
- the amount of the polyether compound having an olefin moiety in the molecule is 1 to 10 equivalents with respect to 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer having iodine at one end of the molecular chain or at both ends of the molecular chain. More preferably, 1.5 to 3 equivalents, and still more preferably about 2 equivalents can be used.
- radical initiator examples include azobisisobutyronitrile (AIBN), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN, VAZO (registered trademark)), di-t-butyl peroxide, t-butylhydro Examples thereof include peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.
- AIBN azobisisobutyronitrile
- ABCN 1,1′-azobis (cyclohexanecarbonitrile)
- VAZO registered trademark
- the radical initiator is used in an amount of 0.1 to 5 equivalents, more preferably 0.1 to 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer having iodine at one end of the molecular chain or both ends of the molecular chain. 5 to 2 equivalents, more preferably about 1 equivalent can be used.
- the solvent examples include a fluorine-based solvent.
- the fluorine-based solvent 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-3-methoxy-2- (trifluoromethyl) pentane and other hydrofluoroether (HFE) solvents (trade name: Novec series, manufactured by 3M) ), A perfluoro solvent composed of a fully fluorinated compound (trade name: Fluorinert series, manufactured by 3M), and the like.
- HFE hydrofluoroether
- the amount of the solvent used is 50 to 300 parts by mass, preferably 150 to 250 parts by mass, more preferably about 100 parts by mass with respect to 100 parts by mass of the fluoropolyether group-containing polymer having iodine at one end of the molecular chain or both ends of the molecular chain. 200 parts by mass can be used.
- the reducing agent examples include hydrides such as sodium borohydride and lithium aluminum hydride, and metals such as iron, zinc, nickel, aluminum, and magnesium.
- the amount of the reducing agent used is 0.5 to 5 equivalents, more preferably 1 to 3 with respect to 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer having iodine at one end of the molecular chain or both ends of the molecular chain.
- An equivalent amount, more preferably about 1.5 equivalents can be used.
- Examples of the reagent that can be used for converting the substituent on the silyl group into a hydrolyzable group include alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol.
- the amount used is 10 to 200 parts by mass with respect to 100 parts by mass of a reaction product of a fluoropolyether group-containing polymer having iodine at one end of the molecular chain or both ends of the molecular chain, an organosilicon compound, and a polyether compound.
- Preferably 40 to 100 parts by mass can be used.
- an organosilicon compound containing a hydroxyl group or hydrolyzable group modified with a fluorooxyalkylene group-containing polymer residue represented by the following general formula (6) and a polyether group and / Or the partial (hydrolysis) condensate can be illustrated.
- Rf, Y, X, R, L, l, n, and ⁇ are the same as above.
- Z is independently a single bond, a siloxane bond, or a silylene group, and a1 is an integer of 1 to 5, preferably Is an integer from 1 to 3.
- Z is independently a single bond, a siloxane bond or a silylene group, specifically, a single bond, a straight chain having 2 to 10 silicon atoms, or a 3 to 10 silicon atoms.
- a bond is a linear organopolysiloxane residue having 2 to 4 silicon atoms, a silalkylene residue or a silarylene residue, and more preferably a single bond.
- siloxane bond and silylene group (silalkylene residue, silarylene residue) of Z include the following groups.
- Examples of the structure of the organosilicon compound containing a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer residue represented by formula (6) and a polyether group include the following structures. (In the formula, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1 + q1 is an integer of 10 to 105. Each unit shown in parentheses may be bonded at random.)
- ⁇ is 1 (that is, Rf is a monovalent fluorooxyalkylene group-containing polymer residue) or ⁇ is 2 (that is, Rf is a divalent fluorooxyalkylene group-containing polymer residue).
- Examples of the method for preparing an organosilicon compound containing a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer residue and a polyether group in the case of a group include the following methods.
- a fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a polyether group is used as a solvent, for example, a fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene.
- an organic silicon compound having a SiH group and a hydrolyzable end group in a molecule such as trimethoxysilane is mixed, and a hydrosilylation reaction catalyst such as a chloroplatinic acid / vinylsiloxane complex in a toluene solution is present in the presence of Aging is carried out at a temperature of 120 ° 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.
- an organosilicon compound containing a hydrolyzable group and a polyether group which is represented by the above formula (6) and is modified with a fluorooxyalkylene group-containing polymer residue when ⁇ is 1 or ⁇ is 2
- the preparation method include the following methods.
- a fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a polyether group is used as a solvent, for example, a fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene.
- hydrosilylation reaction catalyst such as chloroplatinic acid / vinyl siloxane complex Aging at a temperature of 40 to 120 ° 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.
- the substituent (halogen atom) on the silyl group may be converted to, for example, a methoxy group.
- a SiH group-containing organosilicon compound having no hydrolyzable end group can also be used.
- an organosilicon compound having no hydrolyzable end groups in the molecule and having two or more SiH groups can also be used.
- a polymer containing a fluoropolyether group having two olefin moieties at one molecular chain end or both molecular chain ends and having a polyether group, and a hydrolyzable end group in the molecule is a polymer containing a fluoropolyether group having two olefin moieties at one molecular chain end or both molecular chain ends and having a polyether group, and a hydrolyzable end group in the molecule.
- an organosilicon compound having two or more SiH groups After having reacted with an organosilicon compound having two or more SiH groups, it has an olefin moiety and a hydrolyzable end group in the molecule such as SiH group at the polymer end of the reaction product and allyltrimethoxysilane.
- An organosilicon compound is mixed and a hydrosilylation reaction catalyst such as chloroplatinic acid / vinylsiloxane complex in the presence of a toluene solution at a temperature of 40 to 120 ° C., preferably 60 to 100 ° C., more preferably about 80 ° C. Aging is performed for ⁇ 72 hours, preferably 20 to 36 hours, more preferably about 24 hours.
- the fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a polyether group includes a fluoropolyether group represented by the following general formula (10)
- a polymer can be illustrated.
- Rf, Z, L, l, R and ⁇ are the same as above, S is a divalent hydrocarbon group, and the hydrocarbon group may contain a silicon atom and / or a siloxane bond. .
- S is a divalent hydrocarbon group, preferably a divalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms.
- 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.
- C6-C8 such as phenylene group
- an alkylene group containing an arylene group for example, an alkylene / arylene group having 7 to 8 carbon atoms.
- S is preferably a linear alkylene group having 1 to 4 carbon atoms.
- Preferred examples of the fluoropolyether group-containing polymer represented by the formula (10) include those shown below.
- the repeating number (or degree of polymerization) of each repeating unit constituting the fluoropolyether group is the formula (7) in Rf above.
- any number satisfying Expression (8) can be taken.
- r1, p1, and q1 are the same as above. Each unit shown in parentheses may be bonded at random.
- a fluoropolyether group-containing polymer represented by the above formula (10) for example, a fluoropolyether group-containing polymer having two olefin moieties at one molecular chain terminal or both molecular chain terminals and having a hydroxyl group And a polyether group introducing agent in the presence of a base, if necessary using an additive or solvent that improves the reactivity, and a temperature of 0 to 90 ° C., preferably 50 to 80 ° C., more preferably 60 to 70 ° C. And aging for 1 to 48 hours, preferably 10 to 40 hours, more preferably 20 to 30 hours.
- fluoropolyether group-containing polymer represented by the above formula (10) for example, a fluoropolymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a hydroxyl group.
- a molecular chain fragment end or molecule is obtained by performing a dehydrogenation reaction at a temperature of 15 to 35 ° C., more preferably about 25 ° C., for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour.
- a fluoropolyether group-containing polymer having two olefin moieties at both chain ends and having SiH groups is obtained.
- a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain fragment end or both molecular chain ends and having a SiH group, and a polyether compound having an olefin moiety in the molecule (for example, molecular chain fragment Terminal alkenyloxy group-blocked polyalkylene oxide compound) is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene, and a hydrosilylation reaction catalyst such as chloroplatinic acid / vinylsiloxane complex
- aging is carried out at a temperature of 40 to 120 ° 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.
- fluoropolyether group-containing polymer having two olefin sites at one molecular chain end or both molecular chain ends used for the preparation of the fluoropolyether group-containing polymer represented by formula (10)
- Specific examples include those shown below. (In the formula, r1, p1, and q1 are the same as above. Each unit shown in parentheses may be bonded at random.)
- Examples of a method for preparing a fluoropolyether group-containing polymer having two olefin moieties at one end of the molecular chain or both ends of the molecular chain and having a hydroxyl group include an acid fluoride group ( A perfluoropolyether group-containing polymer having —C ( ⁇ O) —F), a Grignard reagent as a nucleophile, and, for example, 1,3-bis (trifluoromethyl) benzene and tetrahydrofuran as a solvent are mixed, and 0-80 C., preferably 50 to 70.degree. C., more preferably about 60.degree. C. for 1 to 6 hours, preferably 3 to 5 hours, more preferably about 4 hours.
- a Grignard reagent as a nucleophile
- the perfluoropolyether group-containing polymer uses an acid halide, an acid anhydride, an ester, a carboxylic acid, an amide or the like in addition to the acid fluoride described above as a group having one end of the molecular chain or both ends of the molecular chain. be able to.
- Specific examples of the perfluoropolyether group-containing polymer having these groups at one end of the molecular chain or at both ends of the molecular chain include the following. (Wherein p1 and q1 are the same as above. Each unit shown in parentheses may be bonded at random)
- nucleophilic agent used for the preparation of a fluoropolyether group-containing polymer having two olefin moieties at one end of the molecular chain or both ends of the molecular chain and having a hydroxyl group allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenylmagnesium 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 perfluoropolyether group-containing polymer. Can be used.
- Examples of the solvent used for the preparation of the fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a hydroxyl group include fluorine-based and non-fluorinated organic solvents.
- fluorine-based organic solvent 1,3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, Hydrofluoroether (HFE) solvents such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane (manufactured by 3M, Product name: Novec series), composed of fully fluorinated compounds That perfluoro-based solvent (3M Co., Ltd., trade name: Fluorinert series), and the like.
- HFE Hydrofluoroether
- ether solvents such as tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used as the non-fluorine organic solvent.
- THF tetrahydrofuran
- monoethylene glycol dimethyl ether diethylene glycol dimethyl ether
- triethylene glycol dimethyl ether triethylene glycol dimethyl ether
- tetraethylene glycol dimethyl ether tetraethylene glycol dimethyl ether
- dioxane dioxane
- fluorinated organic solvent can 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 perfluoropolyether group-containing polymer.
- an aqueous layer and an organic solvent layer are separated by a liquid separation operation.
- the obtained organic solvent layer is more preferably washed with a non-fluorine organic solvent, and the solvent is distilled off to have two olefin sites at one end of the molecular chain or both ends of the molecular chain.
- a fluoropolyether group-containing polymer is obtained.
- a polyether halide can be used, and specifically, 2-bromoethyl methyl ether. Ethylene glycol 2-bromoethyl methyl ether, diethylene glycol 2-bromoethyl methyl ether, triethylene glycol 2-bromoethyl methyl ether, and the like.
- the amount of the polyether group introducing agent used is 1 to 1 equivalent of a reactive end group of a fluoropolyether group-containing polymer having two olefin moieties at one end of the molecular chain or both ends of the molecular chain and having a hydroxyl group. 15 equivalents, more preferably 1.5 to 9 equivalents, still more preferably 2 to 7 equivalents 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 20 equivalents relative to 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a hydroxyl group.
- tetrabutylammonium halide for the preparation of the fluoropolyether group-containing polymer represented by the formula (10), tetrabutylammonium halide, alkali metal halide or the like may be used as an additive for improving the reactivity.
- Specific additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium, tetrabutylammonium hydrogensulfate, sodium iodide, potassium iodide, cesium iodide, crown ether Etc.
- additives improve the reactivity by catalytically exchanging halogens with the olefin introducing agent in the reaction system, and the crown ether coordinates with the metal to improve the reactivity.
- the additive is used in an amount of 0.005 to 0 with respect to 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer having two olefin moieties at one molecular chain terminal or both molecular chain terminals and having a hydroxyl group. .1 equivalent, more preferably 0.01 to 0.05 equivalent, still more preferably about 0.02 equivalent.
- a solvent may be used for the preparation of the fluoropolyether group-containing polymer represented by the formula (10).
- the solvent to be used include fluorine-based and non-fluorine-based organic solvents. Among them, 1,3-bis (trifluoromethyl) benzene, Fluorinated aromatic hydrocarbon solvents such as fluoromethylbenzene, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane, etc.
- Hydrofluoroether (HFE) solvent (trade name: Novec series, manufactured by 3M), perfluoro solvent (trade name: Fluorinert series, manufactured by 3M) composed of fully fluorinated compounds It is done. Further, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, THF, and the like can be used as the non-fluorine organic solvent. Of these organic solvents, it is preferable to use a fluorine organic solvent.
- the amount used in the case of using the organic solvent is 10 to 300 parts by mass with respect to 100 parts by mass of the fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a hydroxyl group.
- 30 to 150 parts by mass, more preferably about 50 parts by mass can be used.
- the organosilicon compound having no hydrolyzable end group in the molecule and having two or more SiH groups used for the preparation of the fluoropolyether group-containing polymer represented by the formula (10) is represented by the following general formula ( Compounds represented by 11) to (13) are preferred.
- R 1 , R 2 , g and j are the same as above. I is an integer of 2 to 9, preferably 2 to 4, and i + j is an integer of 2 to 9.
- organosilicon compound having no hydrolyzable end group in the molecule and having two or more SiH groups examples include the following.
- the amount of the organosilicon compound having no hydrolyzable end group in the molecule and having two or more SiH groups is Alternatively, 7 to 30 equivalents, more preferably 5 to 20 equivalents, and still more preferably 2 equivalents to 1 equivalent of reactive terminal groups of a fluoropolyether group-containing polymer having two olefin moieties at both ends of the molecular chain and having a hydroxyl group About 10 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 amount of the dehydrogenation catalyst used is 0.01 to 1 with respect to 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a hydroxyl group. 0.0005 equivalent, more preferably 0.007 to 0.001 equivalent, and still more preferably about 0.005 equivalent can be used.
- an aqueous layer and an organic solvent layer are separated by a liquid separation operation.
- the obtained organic solvent layer is more preferably washed with a non-fluorine organic solvent, and the solvent is distilled off to have two olefin sites at one end of the molecular chain or both ends of the molecular chain.
- a fluoropolyether group-containing polymer having the following is obtained.
- one end of a molecular chain shown below is blocked with an allyloxy group and the other end is Examples thereof include a polyalkylene oxide compound blocked with a alkenyloxy group blocked at one end of a molecular chain such as polyethylene oxide blocked with a methoxy group. (Wherein l is the same as above)
- the amount of the polyether compound having an olefin moiety in the molecule is 1 equivalent of a reactive end group of a fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a SiH group. 1 to 10 equivalents, more preferably 2 to 5 equivalents, and still more preferably about 3 equivalents can be used.
- platinum black platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefin, aldehyde, vinylsiloxane
- platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, and the like, complexes with acetylene alcohols, and the like.
- platinum compounds such as vinylsiloxane coordination compounds.
- the amount of hydrosilylation reaction catalyst used is in terms of transition metal (mass) relative to the mass of the fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having SiH groups. It is used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm.
- the solvent used is preferably a fluorine-based solvent.
- the fluorine-based solvent include 1,3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, and ethyl nonafluorobutyl ether.
- Hydrofluoroethers such as ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane -Based solvent (made by 3M, trade name: Novec series), fully fluorinated
- a perfluoro solvent composed of a compound (trade name: Fluorinert series, manufactured by 3M Co.) may be used.
- the amount of the solvent used is 10 to 300 parts by mass, preferably 100 to 300 parts by mass, preferably 100 parts by mass of the fluoropolyether group-containing polymer having two olefin moieties at one molecular chain terminal or both molecular chain terminals. 50 to 150 parts by mass, more preferably about 100 parts by mass can be used.
- 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 end group in such a molecule examples include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, and triisopropenoxysilane. , Triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silanes.
- Fluoropolyether group-containing polymer having two olefin sites at one molecular chain end or both molecular chain ends and having a polyether group Fluoropolyether group-containing polymer having two olefin sites at one molecular chain end or both molecular chain ends and having a polyether group, the amount of organosilicon compound having SiH groups and hydrolyzable end groups in the molecule 1 to 4 equivalents, more preferably 1.5 to 3 equivalents, and still more preferably 2 to 2.5 equivalents can be used per 1 equivalent of the reactive end group.
- organic silicon compounds having no hydrolyzable end groups in the molecule and having two or more SiH groups are preferably compounds represented by the following general formulas (11) to (13). (In the formula, R 1 , R 2 , g, j, i, i + j 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.
- organosilicon compound represented by formula (6) In the preparation of an organosilicon compound represented by formula (6) and containing a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer residue and a polyether group when ⁇ is 1 or ⁇ is 2,
- the amount of the organosilicon compound having no hydrolyzable end group in the molecule and having two or more SiH groups has two olefin sites at one end of the molecular chain or both ends of the molecular chain, and has a polyether group. 7 to 30 equivalents, more preferably 5 to 20 equivalents, and still more preferably about 10 equivalents can be used per 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer.
- the organic silicon compound having an olefin moiety and a hydrolyzable end group in the molecule is preferably a compound represented by the following general formula (18). (In the formula, R, X and n are the same as described above. U is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms.)
- U 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.
- the amount of the organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule is a fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a polyether group.
- An equivalent amount, more preferably about 4 equivalents, can be used.
- hydrosilylation reaction catalysts include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and olefins, aldehydes, vinyl siloxane, acetylene alcohols, tetrakis (triphenylphosphine) palladium, Examples thereof include platinum group metal catalysts such as chlorotris (triphenylphosphine) rhodium.
- platinum compounds such as vinylsiloxane coordination compounds.
- the amount of hydrosilylation reaction catalyst used is a fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end or both molecular chain ends and having a polyether group, or a hydrolyzable terminal in the polymer and molecule. Used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm in terms of transition metal, based on the mass of the reaction product with an organosilicon compound having no group and having two or more SiH groups To do.
- the target compound can be obtained by depressurizingly distilling a solvent and an unreacted substance.
- a compound represented by the following formula as a fluoropolyether group-containing polymer having two olefin moieties at one molecular chain end and having a polyether group
- 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.
- a compound represented by the following formula as a fluoropolyether group-containing polymer having two olefin moieties at both ends of the molecular chain and having a polyether group
- 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 components (A) and (B) may be synthesized from the raw material for synthesizing the component (A) in the state where the component (B) is previously included,
- the component (B) may be synthesized in a state in which the component (A) is previously included in the raw material for synthesizing the component.
- the present invention includes (A) a hydroxyl group or hydrolyzable group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer residue and / or a partial (hydrolyzed) condensate thereof; and (B) fluorooxyalkylene.
- a surface treatment agent containing a fluorine-containing coating agent composition mixed at a mixing mass ratio ((A) :( B)) of 15:85 to 85:15.
- the surface treating agent is a portion obtained by condensing a hydroxyl group of the fluoropolyether group-containing polymer or a hydroxyl group obtained by partially hydrolyzing a terminal hydrolyzable group of the fluoropolyether group-containing polymer in advance by a known method. (Hydrolysis) Condensate may be included.
- the surface treatment agent may be a hydrolytic 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.
- acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid and the like are particularly desirable.
- the addition amount of the hydrolysis-condensation catalyst is a catalytic amount, and is usually 0.01 to 5 parts by weight, particularly 0.1 to 1 part by weight, based on a total of 100 parts by weight of the components (A) and (B). .
- 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 optimum concentration of the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate 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 parts by weight, particularly 0.05 to 5 parts by weight, based on 100 parts by weight of the total of the fluoropolyether group-containing polymer (and its part (hydrolyzed) condensate). In this case, the amount is preferably 1 to 100 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight in total of the solvent and the components (A) and (B).
- 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 and curing time vary depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), 25 to 200 ° C., particularly 25 to 80 ° C., 30 minutes to 36 hours. In particular, it is preferably 1 to 24 hours. Further, in the case of applying by vapor deposition, it is desirable that the temperature is 20 to 200 ° C., particularly 25 to 120 ° C., 30 minutes to 48 hours, particularly 1 to 24 hours.
- 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. Further, for example, in spray coating, if the coating is diluted with a fluorine-based solvent to which moisture has been added in advance to generate hydrolysis, that is, Si—OH, and then spray coating is performed, curing after coating is fast.
- a fluorine-based solvent to which moisture has been added in advance to generate hydrolysis that is, Si—OH
- 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 phone, smartphone, digital camera, digital video camera, PDA, portable audio player, car audio, game device, spectacle lens, camera lens, lens filter,
- the optical articles include medical equipment such as sunglasses and a stomach camera, a copying machine, a PC, a liquid crystal display, an organic EL display, a plasma display, a touch panel display, a protective film, and an antireflection film. 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, aircraft, etc., antifouling coating for headlamp covers, etc.
- component (A) component fluorooxyalkylene group-containing polymer-modified silane compound hydrolysable group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer residue
- the following compounds [Compound 1] to [Compound 3] ]) was prepared. In the formula, each unit shown in parentheses is randomly connected. [Compound 1] [Compound 2] [Compound 3]
- component (B) component fluorooxyalkylene group-containing polymer-modified silane compound an organosilicon compound containing a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer residue and a polyether group
- compound 4 an organosilicon compound containing a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer residue and a polyether group
- the fluoropolyether group-containing polymer of compounds 1 to 3 and the fluoropolyether group-containing polymer of compound 4 are adjusted to a concentration of 20% by mass with Novec 7200.
- a surface treatment agent was prepared by dissolving in (3M, ethyl perfluorobutyl ether). 4 ⁇ l of each surface treatment agent was vacuum-deposited on a glass (Gorilla manufactured by Corning) with 10 nm of SiO 2 treated on the outermost surface (treatment conditions: pressure: 2.0 ⁇ 10 ⁇ 2 Pa, heating temperature: 700 ° C.) Curing was performed for 12 hours in an atmosphere of 25 ° C. and humidity of 40% RH to form a cured film having a thickness of 8 nm.
- the adhesiveness to the substrate was obtained by mixing a polymer having a hydrolyzable group (alkoxy group) at the terminal and a polymer having a polyether group and a hydrolyzable group (alkoxy group) at the terminal. And wettability improved. Therefore, the cured coatings of the surface treatment agents of Examples 1 to 4 maintained a contact angle of 100 ° or more after 5,000 times of wear of steel wool and 3,000 times of wear of eraser. Compared to the cured film of the surface treatment agent of No. 3, it exhibited excellent wear resistance.
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Abstract
Description
〔1〕
(A)フルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び/又はその部分(加水分解)縮合物と、(B)フルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基とポリエーテル基を含有する有機ケイ素化合物及び/又はその部分(加水分解)縮合物とを含み、(A)成分と(B)成分との混合質量比が15:85~85:15(但し、(A)成分と(B)成分との合計は100)であることを特徴とする含フッ素コーティング剤組成物。
〔2〕
(A)成分が、下記一般式(1)
で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び/又はその部分(加水分解)縮合物であり、
(B)成分が、下記一般式(2)又は(3)
Rf-[N(V)β(E)γ]α (2)
(式中、Rf、αは上記と同じであり、Nは独立に酸素原子、ケイ素原子もしくは窒素原子を含んでいてもよく、フッ素置換されていてもよい3~8価の有機基であり、Vは独立に末端に水酸基又は加水分解性基を有する1価の基であり、Eは独立にオキシアルキレン基を有する1価の基であり、βは1~6の整数、γは1~6の整数で、β+γは2~7の整数である。)
Rf-[Q-(G)δ-(E’)ε-B]α (3)
(式中、Rf、αは上記と同じであり、Qは独立に単結合又は2価の有機基であり、Gは独立に水酸基又は加水分解性基を有する2価の基であり、E’は独立にオキシアルキレン基を有する2価の基であり、水酸基又は加水分解性基を有していてもよい。Bは独立に水素原子、炭素数1~4のアルキル基又はハロゲン基であり、δは独立に0~10の整数であり、εは独立に1~10の整数である。なお、上記GとE’は直鎖状に連結しており、これらG、E’はそれぞれランダムに配列されていてよい。)
で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基とポリエーテル基を含有する有機ケイ素化合物及び/又はその部分(加水分解)縮合物である〔1〕記載の含フッ素コーティング剤組成物。
〔3〕
(A)成分が、下記一般式(4)又は(5)
で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び/又はその部分(加水分解)縮合物であり、
(B)成分が、下記一般式(6)
で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基とポリエーテル基を含有する有機ケイ素化合物及び/又はその部分(加水分解)縮合物である〔2〕記載の含フッ素コーティング剤組成物。
〔4〕
前記式(1)~(6)のαが1であり、Rf基が下記一般式(7)で表される1価のフルオロオキシアルキレン基含有ポリマー残基であることを特徴とする〔2〕又は〔3〕に記載の含フッ素コーティング剤組成物。
〔5〕
前記式(1)~(6)のαが2であり、Rf基が下記一般式(8)で表される2価のフルオロオキシアルキレン基含有ポリマー残基であることを特徴とする〔2〕又は〔3〕記載の含フッ素コーティング剤組成物。
〔6〕
前記式(4)、(6)において、Yがそれぞれ、炭素数3~10のアルキレン基、炭素数6~8のアリーレン基を含む炭素数2~8のアルキレン基、炭素数2~8のアルキレン基相互が炭素数1~4のシルアルキレン構造又は炭素数6~10のシルアリーレン構造を介して結合している2価の基、及びケイ素原子数2~10個の直鎖状又はケイ素原子数3~10個の分岐状もしくは環状の2~4価のオルガノポリシロキサン残基の結合手に炭素数2~10のアルキレン基が結合している2~4価の基からなる群より選ばれる基である〔3〕~〔5〕のいずれかに記載の含フッ素コーティング剤組成物。
〔7〕
前記式(4a)において、Y’が、炭素数2~10のアルキレン基、炭素数6~8のアリーレン基を含む炭素数2~8のアルキレン基、ジオルガノシリレン基を含む炭素数2~6のアルキレン基、炭素数2~8のアルキレン基相互が炭素数1~4のシルアルキレン構造又は炭素数6~10のシルアリーレン構造を介して結合している2価の基、ケイ素原子数2~10個の直鎖状の2価のオルガノポリシロキサン残基を含む炭素数2~6のアルキレン基、及びケイ素原子数2~10個の直鎖状又はケイ素原子数3~10個の分岐状もしくは環状の2~4価のオルガノポリシロキサン残基の結合手に炭素数2~10のアルキレン基が結合している2~4価の基からなる群より選ばれる基である〔3〕~〔6〕のいずれかに記載の含フッ素コーティング剤組成物。
〔8〕
前記式(6)において、Zが、単結合、ケイ素原子数2~10個の直鎖状又はケイ素原子数3~10個の分岐状もしくは環状の2~4価のオルガノポリシロキサン残基、及びケイ素原子数2~10個の直鎖状のシルアルキレン残基又はシルアリーレン残基からなる群より選ばれる基である〔3〕~〔7〕のいずれかに記載の含フッ素コーティング剤組成物。
〔9〕
前記式(1)、(4)~(6)において、Xがそれぞれ、水酸基、炭素数1~10のアルコキシ基、炭素数2~10のアルコキシアルコキシ基、炭素数1~10のアシロキシ基、炭素数2~10のアルケニルオキシ基、及びハロゲン基からなる群より選ばれる〔2〕~〔8〕のいずれかに記載の含フッ素コーティング剤組成物。
〔10〕
式(1)で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された加水分解性基含有有機ケイ素化合物が、下記式のいずれかで表されるものである〔2〕~〔9〕のいずれかに記載の含フッ素コーティング剤組成物。
〔11〕
式(2)、(3)で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された加水分解性基とポリエーテル基を含有する有機ケイ素化合物が、下記式のいずれかで表されるものである〔2〕~〔10〕のいずれかに記載の含フッ素コーティング剤組成物。
〔12〕
〔1〕~〔11〕のいずれかに記載の含フッ素コーティング剤組成物を含有する表面処理剤。
〔13〕
〔12〕に記載の表面処理剤で表面処理された物品。
(A)成分は、フルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び/又はその部分(加水分解)縮合物(即ち、該有機ケイ素化合物を部分的に(加水分解)縮合して生成する、分子中に2個以上、好ましくは3個以上の残存水酸基もしくは加水分解性基を有するオルガノシロキサンオリゴマー)であり、好適には、下記一般式(1)で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び/又はその部分(加水分解)縮合物である。
また、dは単位毎にそれぞれ独立して0~3の整数であり、好ましくは1又は2であり、該単位は直鎖状であっても分岐状であってもよい。
Yとして、具体的には、プロピレン基(トリメチレン基、メチルエチレン基)、ブチレン基(テトラメチレン基、メチルプロピレン基)、ヘキサメチレン基等の炭素数3~10のアルキレン基、フェニレン基等の炭素数6~8のアリーレン基を含む炭素数2~8のアルキレン基(例えば、炭素数8~16のアルキレン・アリーレン基等)、炭素数2~8のアルキレン基相互が炭素数1~4のシルアルキレン構造又は炭素数6~10のシルアリーレン構造を介して結合している2価の基、ケイ素原子数2~10個、好ましくは2~5個の直鎖状、分岐状又は環状の2~6価のオルガノポリシロキサン残基の結合手に炭素数2~10のアルキレン基が結合している2~6価の基などが挙げられ、好ましくは炭素数3~10のアルキレン基、フェニレン基を含む炭素数2~6のアルキレン基、炭素数2~4のアルキレン基相互が炭素数1~4のシルアルキレン構造又は炭素数6~10のシルアリーレン構造を介して結合している2価の基、ケイ素原子数2~10個の直鎖状又はケイ素原子数3~10個の分岐状もしくは環状の2~4価のオルガノポリシロキサン残基の結合手に炭素数2~10のアルキレン基が結合している2~4価の基であり、更に好ましくは炭素数3~6のアルキレン基である。
Y’として、具体的には、エチレン基、プロピレン基(トリメチレン基、メチルエチレン基)、ブチレン基(テトラメチレン基、メチルプロピレン基)、ヘキサメチレン基等の炭素数2~10のアルキレン基、フェニレン基等の炭素数6~8のアリーレン基を含む炭素数2~8のアルキレン基(例えば、炭素数8~16のアルキレン・アリーレン基等)、ジメチルシリレン基やジエチルシリレン基等のジオルガノシリレン基を含む炭素数2~6のアルキレン基、炭素数2~8のアルキレン基相互が炭素数1~4のシルアルキレン構造又は炭素数6~10のシルアリーレン構造を介して結合している2価の基、ケイ素原子数2~10個、好ましくは2~5個の直鎖状、分岐状又は環状の2~6価のオルガノポリシロキサン残基を含む炭素数2~6のアルキレン基、ケイ素原子数2~10個、好ましくは2~5個の直鎖状、分岐状又は環状の2~6価のオルガノポリシロキサン残基の結合手に炭素数2~10のアルキレン基が結合している2~6価の基などが挙げられ、好ましくは炭素数3~10のアルキレン基、フェニレン基を含む炭素数2~6のアルキレン基、ジメチルシリレン基を含む炭素数2~6のアルキレン基、炭素数2~4のアルキレン基相互が炭素数1~4のシルアルキレン構造又は炭素数6~10のシルアリーレン構造を介して結合している2価の基、ケイ素原子数2~10個の直鎖状の2価のオルガノポリシロキサン残基を含む炭素数2~6のアルキレン基、ケイ素原子数2~10個の直鎖状又はケイ素原子数3~10個の分岐状もしくは環状の2~4価のオルガノポリシロキサン残基の結合手に炭素数2~10のアルキレン基が結合している2~4価の基であり、更に好ましくは炭素数3~6のアルキレン基である。
また、Xは水酸基又は加水分解性基である。このようなXとしては、水酸基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などの炭素数1~10のアルコキシ基、メトキシメトキシ基、メトキシエトキシ基などの炭素数2~10のアルコキシアルコキシ基、アセトキシ基などの炭素数1~10のアシロキシ基、イソプロペノキシ基などの炭素数2~10のアルケニルオキシ基などが挙げられる。中でもメトキシ基、エトキシ基が好適である。
nは1~3の整数であり、好ましくは2又は3であり、より好ましくは3である。mは1~6の整数であり、好ましくは1~4の整数であり、aは1~5の整数であり、好ましくは1~3の整数であり、より好ましくは1である。αは1又は2である。
(B)成分は、フルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基とポリエーテル基を含有する有機ケイ素化合物及び/又はその部分(加水分解)縮合物であり、好適には、下記一般式(2)又は(3)
Rf-[N(V)β(E)γ]α (2)
(式中、Rf、αは上記と同じであり、Nは独立に酸素原子、ケイ素原子もしくは窒素原子を含んでいてもよく、フッ素置換されていてもよい3~8価の有機基であり、Vは独立に末端に水酸基又は加水分解性基を有する1価の基であり、Eは独立にオキシアルキレン基を有する1価の基であり、βは1~6の整数、γは1~6の整数で、β+γは2~7の整数である。)
Rf-[Q-(G)δ-(E’)ε-B]α (3)
(式中、Rf、αは上記と同じであり、Qは独立に単結合又は2価の有機基であり、Gは独立に水酸基又は加水分解性基を有する2価の基であり、E’は独立にオキシアルキレン基を有する2価の基であり、水酸基又は加水分解性基を有していてもよい。Bは独立に水素原子、炭素数1~4のアルキル基又はハロゲン基であり、δは独立に0~10の整数であり、εは独立に1~10の整数である。なお、上記GとE’は直鎖状に連結しており、これらG、E’はそれぞれランダムに配列されていてよい。)
で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基とポリエーテル基を含有する有機ケイ素化合物及び/又はその部分(加水分解)縮合物である。
なお、(A)成分は化合物中にフルオロポリエーテル基(フルオロオキシアルキレン基)以外に非置換のポリエーテル基を含有しないものであるのに対し、(B)成分は化合物中にフルオロポリエーテル基以外にもポリエーテル基(即ち、非置換のポリエーテル基)を有するものであり、この点で(A)成分と(B)成分は相違するものである。
また、上記式(3)において、δは0~10の整数、好ましくは1~4の整数である。δが0である場合、E’は水酸基又は加水分解性基を有する。εは1~10の整数、好ましくは1~4の整数である。なお、上記GとE’は直鎖状に連結しており、これらG、E’はそれぞれランダムに配列されていてよい。
分子鎖片末端又は分子鎖両末端にポリエーテル基とオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、例えばトリクロロシランやトリアルコキシシラン等の分子中にSiH基及び加水分解性末端基(ハロゲン原子やアルコキシ基等)を有する有機ケイ素化合物を混合し、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは20~36時間、より好ましくは約24時間熟成させる。なお、分子中にSiH基及び加水分解性末端基を有する有機ケイ素化合物として、トリクロロシラン等のSiH基含有ハロゲン化(有機)ケイ素化合物を用いた場合は、その後、シリル基上の置換基(ハロゲン原子)を、他の加水分解性基として例えばメトキシ基などのアルコキシ基等に変換してもよい。
続いて、上記分子鎖片末端又は分子鎖両末端にSiH基とオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマーと、分子内にオレフィン部位を有するポリエーテル化合物(例えば、分子鎖片末端アルケニルオキシ基封鎖ポリアルキレンオキシド化合物等)とを、分子鎖片末端又は分子鎖両末端にSiH基とオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマーのSiH基1当量に対して、分子内にオレフィン部位を有するポリエーテル化合物を1~10当量、より好ましくは2~5当量、更に好ましくは約3当量用い、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは20~36時間、より好ましくは約24時間熟成させる。
この使用量は、分子鎖片末端又は分子鎖両末端にポリエーテル基とオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマーとSiH基含有ハロゲン化(有機)ケイ素化合物との付加反応生成物100質量部に対して、10~200質量部、より好ましくは40~100質量部、更に好ましくは65質量部用いることができる。
溶剤の使用量は、分子鎖片末端又は分子鎖両末端にポリエーテル基とオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマー100質量部に対して、10~300質量部、好ましくは50~150質量部、更に好ましくは約100質量部用いることができる。
ヒドロシリル化反応触媒の使用量は、分子鎖片末端又は分子鎖両末端にポリエーテル基とオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマーの質量に対して、遷移金属換算(質量)で0.1~100ppm、より好ましくは1~50ppmとなる量で使用する。
分子鎖片末端又は分子鎖両末端にオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、トリクロロシラン等の分子中にSiH基及び加水分解性末端基を有するSiH基含有ハロゲン化(有機)ケイ素化合物を混合し、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは20~36時間、より好ましくは約24時間熟成させた後、更に、シリル基上の置換基(ハロゲン原子)をポリエーテル基と、加水分解性基として例えばメトキシ基などとに変換する。
分子中にSiH基及び加水分解性末端基を有するSiH基含有ハロゲン化(有機)ケイ素化合物の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマーのオレフィン部位1当量に対して、1~4当量、より好ましくは1.5~2.5当量、更に好ましくは約2当量となるように用いることができる。
使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマーと分子中にSiH基及び加水分解性末端基を有するSiH基含有ハロゲン化(有機)ケイ素化合物との付加反応生成物100質量部に対して、5~100質量部、より好ましくは20~50質量部、更に好ましくは35質量部用いることができる。
使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマーと分子中にSiH基及び加水分解性末端基を有するSiH基含有ハロゲン化(有機)ケイ素化合物との付加反応生成物100質量部に対して、10~200質量部、より好ましくは40~100質量部、更に好ましくは65質量部用いることができる。
溶剤の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマー100質量部に対して、10~300質量部、好ましくは50~150質量部、更に好ましくは約100質量部用いることができる。
ヒドロシリル化反応触媒の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を1つ以上有するフルオロポリエーテル基含有ポリマーの質量に対して、遷移金属換算(質量)で0.1~100ppm、より好ましくは1~50ppmとなる量で使用する。
分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ以上有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、まず、分子中にSiH基及びポリオキシアルキレン基を有する有機ケイ素化合物を混合し、フルオロポリエーテル基含有ポリマーのオレフィン部位の一部とポリオキシアルキレン基及びSiH基含有有機ケイ素化合物のSiH基とを反応させるため、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは20~36時間、より好ましくは約24時間熟成させる。続いて、トリメトキシシラン等の分子中にSiH基及び加水分解性末端基(アルコキシ基等)を有する有機ケイ素化合物を混合し、残ったフルオロポリエーテル基含有ポリマーのオレフィン部位と有機ケイ素化合物のSiH基とを反応させるため、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは20~36時間、より好ましくは約24時間熟成させる。
なお、分子中にSiH基及び加水分解性末端基を有する有機ケイ素化合物として、トリクロロシラン等のSiH基含有ハロゲン化(有機)ケイ素化合物を用いた場合は、その後、シリル基上の置換基(ハロゲン原子)を、他の加水分解性基として例えばメトキシ基などのアルコキシ基等に変換してもよい。
溶剤の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ以上有するフルオロポリエーテル基含有ポリマー100質量部に対して、10~300質量部、好ましくは50~150質量部、更に好ましくは約100質量部用いることができる。
ヒドロシリル化反応触媒の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ以上有するフルオロポリエーテル基含有ポリマーの質量に対して、遷移金属換算(質量)で0.1~100ppm、より好ましくは1~50ppmとなる量で使用する。
分子鎖片末端又は分子鎖両末端にヨウ素を有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、ジ-t-ブチルペルオキシドなどのラジカル開始剤を添加した後、ビニルトリクロロシランやビニルトリアルコキシシラン等の分子中にオレフィン部位及び加水分解性末端基を有する有機ケイ素化合物と、分子内にオレフィン部位を有するポリエーテル化合物とを添加し、混合する。この際、60~180℃、好ましくは90~150℃、より好ましくは約120℃の温度で、1~20時間、好ましくは2~10時間、より好ましくは約6時間熟成させることにより、分子鎖片末端又は分子鎖両末端にヨウ素を有するフルオロポリエーテル基含有ポリマーの末端ヨウ素原子を起点として、分子中にオレフィン部位及び加水分解性末端基を有する有機ケイ素化合物と分子内にオレフィン部位を有するポリエーテル化合物とのテロメリゼーションを行う。ここで、分子中にオレフィン部位及び加水分解性末端基を有する有機ケイ素化合物と分子内にオレフィン部位を有するポリエーテル化合物は同時に添加してもよく、また、先にどちらかを反応させた後、もう一方を反応させてもよい。また、分子内にオレフィン部位を有するポリエーテル化合物は、水酸基又は加水分解性基を有していてもよく、水酸基又は加水分解性基を有している場合、分子中にオレフィン部位及び加水分解性末端基を有する有機ケイ素化合物を用いずに、分子内にオレフィン部位を有するポリエーテル化合物のみを用いて製造してもよい。その後、テロメリゼーション化されたフルオロポリエーテル基含有ポリマー末端のヨウ素を金属亜鉛等の還元剤で還元させる。なお、分子中にオレフィン部位及び加水分解性末端基を有する有機ケイ素化合物として、ビニルトリクロロシラン等のオレフィン含有ハロゲン化有機ケイ素化合物を用いた場合は、その後、シリル基上の置換基(ハロゲン原子)を、他の加水分解性基として例えばメトキシ基などのアルコキシ基等に変換してもよい。
分子内にオレフィン部位を有するポリエーテル化合物の使用量は、分子鎖片末端又は分子鎖両末端にヨウ素を有するフルオロポリエーテル基含有ポリマーの反応性末端基1当量に対して、1~10当量、より好ましくは1.5~3当量、更に好ましくは約2当量用いることができる。
ラジカル開始剤の使用量は、分子鎖片末端又は分子鎖両末端にヨウ素を有するフルオロポリエーテル基含有ポリマーの反応性末端基1当量に対して、0.1~5当量、より好ましくは0.5~2当量、更に好ましくは約1当量用いることができる。
溶剤の使用量は、分子鎖片末端又は分子鎖両末端にヨウ素を有するフルオロポリエーテル基含有ポリマー100質量部に対して、50~300質量部、好ましくは150~250質量部、更に好ましくは約200質量部用いることができる。
還元剤の使用量は、分子鎖片末端又は分子鎖両末端にヨウ素を有するフルオロポリエーテル基含有ポリマーの反応性末端基1当量に対して、0.5~5当量、より好ましくは1~3当量、更に好ましくは約1.5当量用いることができる。
使用量は、分子鎖片末端又は分子鎖両末端にヨウ素を有するフルオロポリエーテル基含有ポリマーと有機ケイ素化合物とポリエーテル化合物との反応生成物100質量部に対して、10~200質量部、より好ましくは40~100質量部用いることができる。
分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、ポリエーテル基を有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、トリメトキシシラン等の分子中にSiH基及び加水分解性末端基を有する有機ケイ素化合物を混合し、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは20~36時間、より好ましくは約24時間熟成させる。
分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、ポリエーテル基を有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、トリクロロシラン等の分子中にSiH基及び加水分解性末端基(ハロゲン原子)を有する有機ケイ素化合物を混合し、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは20~36時間、より好ましくは約24時間熟成させる。なお、熟成させた後、シリル基上の置換基(ハロゲン原子)を例えばメトキシ基などに変換してもよい。
続いて、上記分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、SiH基を有するフルオロポリエーテル基含有ポリマーと、分子内にオレフィン部位を有するポリエーテル化合物(例えば、分子鎖片末端アルケニルオキシ基封鎖ポリアルキレンオキシド化合物等)とを溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは20~36時間、より好ましくは約24時間熟成させる。
分子鎖片末端又は分子鎖両末端にこれらの基を有するパーフルオロポリエーテル基含有ポリマーとして、具体的には、下記に示すものが挙げられる。
求核剤の使用量は、上記パーフルオロポリエーテル基含有ポリマーの反応性末端基1当量に対して、2~5当量、より好ましくは2.5~3.5当量、更に好ましくは約3当量用いることができる。
上記有機溶剤の使用量は、上記パーフルオロポリエーテル基含有ポリマー100質量部に対して、10~300質量部、好ましくは100~200質量部、更に好ましくは約150質量部用いることができる。
ポリエーテル基導入剤の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、水酸基を有するフルオロポリエーテル基含有ポリマーの反応性末端基1当量に対して、1~15当量、より好ましくは1.5~9当量、更に好ましくは2~7当量用いることができる。
塩基の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、水酸基を有するフルオロポリエーテル基含有ポリマーの反応性末端基1当量に対して、1~20当量、より好ましくは10~18当量、更に好ましくは約15当量用いることができる。
添加剤の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、水酸基を有するフルオロポリエーテル基含有ポリマーの反応性末端基1当量に対して、0.005~0.1当量、より好ましくは0.01~0.05当量、更に好ましくは約0.02当量用いることができる。
上記有機溶剤を用いる場合の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、水酸基を有するフルオロポリエーテル基含有ポリマー100質量部に対して、10~300質量部、好ましくは30~150質量部、更に好ましくは約50質量部用いることができる。
脱水素触媒の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、水酸基を有するフルオロポリエーテル基含有ポリマーの反応性末端基1当量に対して、0.01~0.0005当量、より好ましくは0.007~0.001当量、更に好ましくは約0.005当量用いることができる。
分子内にオレフィン部位を有するポリエーテル化合物の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、SiH基を有するフルオロポリエーテル基含有ポリマーの反応性末端基1当量に対して、1~10当量、より好ましくは2~5当量、更に好ましくは約3当量用いることができる。
ヒドロシリル化反応触媒の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、SiH基を有するフルオロポリエーテル基含有ポリマーの質量に対して、遷移金属換算(質量)で0.1~100ppm、より好ましくは1~50ppmとなる量で使用する。
溶剤の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、ポリエーテル基を有するフルオロポリエーテル基含有ポリマー100質量部に対して、10~300質量部、好ましくは50~150質量部、更に好ましくは約100質量部用いることができる。
ヒドロシリル化反応触媒の使用量は、分子鎖片末端又は分子鎖両末端にオレフィン部位を2つ有し、ポリエーテル基を有するフルオロポリエーテル基含有ポリマー、又はこのポリマーと分子中に加水分解性末端基を有さず、SiH基を2個以上有する有機ケイ素化合物との反応物の質量に対して、遷移金属換算(質量)で0.1~100ppm、より好ましくは1~50ppmとなる量で使用する。
例えば、分子鎖片末端にオレフィン部位を2つ有し、ポリエーテル基を有するフルオロポリエーテル基含有ポリマーとして、下記式で表される化合物
加水分解縮合触媒の添加量は触媒量であり、通常、上記(A)、(B)成分の合計100質量部に対して0.01~5質量部、特に0.1~1質量部である。
[化合物1]
[化合物4]
[合成例1]
反応容器に、下記式(A)
δ2.3-2.5(C-CH 2 CH=CH2)4H
δ3.1-3.2(-O-(CH2CH2O)3-O-CH 3 )3H
δ3.3-3.7(-O-(CH 2 CH 2 O)3-O-CH3)12H
δ4.9-5.0(-CH2CH=CH 2 )4H
δ5.7-5.8(-CH2CH=CH2)2H
δ0.4-0.6(-CH2CH2CH 2 -Si)4H
δ1.4-1.8(-CH 2 CH 2 CH2-Si)8H
δ3.1-3.2(-O-(CH2CH2O)3-O-CH 3 )3H
δ3.3-3.7(-O-(CH 2 CH 2 O)3-O-CH3、-Si(OCH 3 )3)30H
表1に示す混合割合で、化合物1~3のフルオロポリエーテル基含有ポリマー及び化合物4のフルオロポリエーテル基含有ポリマーを、濃度20質量%になるようにNovec7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
最表面にSiO2を10nm処理したガラス(コーニング社製 Gorilla)に、各表面処理剤4μlを真空蒸着し(処理条件は、圧力:2.0×10-2Pa、加熱温度:700℃)、25℃、湿度40%RHの雰囲気下で12時間硬化させて膜厚8nmの硬化被膜を形成した。
[初期撥水性の評価]
上記にて作製した硬化被膜を形成したガラスについて、接触角計Drop Master(協和界面科学社製)を用いて、硬化被膜の水に対する接触角(撥水性)を測定した(液滴:2μl、温度:25℃、湿度:40%RH)。結果(初期水接触角)を表2に示す。
初期においては、実施例、比較例共に良好な撥水性を示した。
上記にて作製した硬化被膜を形成したガラスについて、ラビングテスター(新東科学社製)を用いて、下記条件でスチールウールは5,000回擦った後、消しゴムは3,000回擦った後の硬化被膜の水に対する接触角(撥水性)を上記と同様にして測定し、耐摩耗性の評価とした。試験環境条件は25℃、湿度40%RHである。結果(摩耗後水接触角)を表2に示す。
耐スチールウール摩耗性
スチールウール:BONSTAR#0000(日本スチールウール社製)
移動距離(片道):30mm
移動速度:3,600mm/分
荷重:1kg/cm2
耐消しゴム摩耗性
消しゴム:Rubber Eraser(Minoan社製)
接触面積:6mmφ
移動距離(片道):30mm
移動速度:3,600mm/分
荷重:1kg/6mmφ
Claims (13)
- (A)フルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び/又はその部分(加水分解)縮合物と、(B)フルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基とポリエーテル基を含有する有機ケイ素化合物及び/又はその部分(加水分解)縮合物とを含み、(A)成分と(B)成分との混合質量比が15:85~85:15(但し、(A)成分と(B)成分との合計は100)であることを特徴とする含フッ素コーティング剤組成物。
- (A)成分が、下記一般式(1)
で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び/又はその部分(加水分解)縮合物であり、
(B)成分が、下記一般式(2)又は(3)
Rf-[N(V)β(E)γ]α (2)
(式中、Rf、αは上記と同じであり、Nは独立に酸素原子、ケイ素原子もしくは窒素原子を含んでいてもよく、フッ素置換されていてもよい3~8価の有機基であり、Vは独立に末端に水酸基又は加水分解性基を有する1価の基であり、Eは独立にオキシアルキレン基を有する1価の基であり、βは1~6の整数、γは1~6の整数で、β+γは2~7の整数である。)
Rf-[Q-(G)δ-(E’)ε-B]α (3)
(式中、Rf、αは上記と同じであり、Qは独立に単結合又は2価の有機基であり、Gは独立に水酸基又は加水分解性基を有する2価の基であり、E’は独立にオキシアルキレン基を有する2価の基であり、水酸基又は加水分解性基を有していてもよい。Bは独立に水素原子、炭素数1~4のアルキル基又はハロゲン基であり、δは独立に0~10の整数であり、εは独立に1~10の整数である。なお、上記GとE’は直鎖状に連結しており、これらG、E’はそれぞれランダムに配列されていてよい。)
で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基とポリエーテル基を含有する有機ケイ素化合物及び/又はその部分(加水分解)縮合物である請求項1記載の含フッ素コーティング剤組成物。 - (A)成分が、下記一般式(4)又は(5)
で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び/又はその部分(加水分解)縮合物であり、
(B)成分が、下記一般式(6)
で表されるフルオロオキシアルキレン基含有ポリマー残基で変性された水酸基もしくは加水分解性基とポリエーテル基を含有する有機ケイ素化合物及び/又はその部分(加水分解)縮合物である請求項2記載の含フッ素コーティング剤組成物。 - 前記式(4)、(6)において、Yがそれぞれ、炭素数3~10のアルキレン基、炭素数6~8のアリーレン基を含む炭素数2~8のアルキレン基、炭素数2~8のアルキレン基相互が炭素数1~4のシルアルキレン構造又は炭素数6~10のシルアリーレン構造を介して結合している2価の基、及びケイ素原子数2~10個の直鎖状又はケイ素原子数3~10個の分岐状もしくは環状の2~4価のオルガノポリシロキサン残基の結合手に炭素数2~10のアルキレン基が結合している2~4価の基からなる群より選ばれる基である請求項3~5のいずれか1項に記載の含フッ素コーティング剤組成物。
- 前記式(4a)において、Y’が、炭素数2~10のアルキレン基、炭素数6~8のアリーレン基を含む炭素数2~8のアルキレン基、ジオルガノシリレン基を含む炭素数2~6のアルキレン基、炭素数2~8のアルキレン基相互が炭素数1~4のシルアルキレン構造又は炭素数6~10のシルアリーレン構造を介して結合している2価の基、ケイ素原子数2~10個の直鎖状の2価のオルガノポリシロキサン残基を含む炭素数2~6のアルキレン基、及びケイ素原子数2~10個の直鎖状又はケイ素原子数3~10個の分岐状もしくは環状の2~4価のオルガノポリシロキサン残基の結合手に炭素数2~10のアルキレン基が結合している2~4価の基からなる群より選ばれる基である請求項3~6のいずれか1項に記載の含フッ素コーティング剤組成物。
- 前記式(6)において、Zが、単結合、ケイ素原子数2~10個の直鎖状又はケイ素原子数3~10個の分岐状もしくは環状の2~4価のオルガノポリシロキサン残基、及びケイ素原子数2~10個の直鎖状のシルアルキレン残基又はシルアリーレン残基からなる群より選ばれる基である請求項3~7のいずれか1項に記載の含フッ素コーティング剤組成物。
- 前記式(1)、(4)~(6)において、Xがそれぞれ、水酸基、炭素数1~10のアルコキシ基、炭素数2~10のアルコキシアルコキシ基、炭素数1~10のアシロキシ基、炭素数2~10のアルケニルオキシ基、及びハロゲン基からなる群より選ばれる請求項2~8のいずれか1項に記載の含フッ素コーティング剤組成物。
- 請求項1~11のいずれか1項に記載の含フッ素コーティング剤組成物を含有する表面処理剤。
- 請求項12に記載の表面処理剤で表面処理された物品。
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