WO2012081524A1 - Composé fluoré, composition de revêtement, matériau de base comportant une couche hydrophobe, et son procédé de production - Google Patents

Composé fluoré, composition de revêtement, matériau de base comportant une couche hydrophobe, et son procédé de production Download PDF

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WO2012081524A1
WO2012081524A1 PCT/JP2011/078612 JP2011078612W WO2012081524A1 WO 2012081524 A1 WO2012081524 A1 WO 2012081524A1 JP 2011078612 W JP2011078612 W JP 2011078612W WO 2012081524 A1 WO2012081524 A1 WO 2012081524A1
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water
integer
compound
group
substrate
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PCT/JP2011/078612
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Japanese (ja)
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星野　泰輝
洋介 竹田
知子 岸川
信行 音澤
白川　大祐
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旭硝子株式会社
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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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

Definitions

  • the present invention relates to a fluorine-containing compound, a coating composition using the fluorine-containing compound, a substrate having a water-repellent layer formed from the coating composition, and a method for producing the same.
  • a water / oil repellent composition containing a fluorine-containing compound having a perfluoroalkyl group and a hydrolyzable silyl group and a solvent is applied to the substrate and dried to repel the substrate.
  • Methods for forming an aqueous film are known.
  • the water / oil repellent composition include a water repellent composition for automobile glass.
  • the water repellent layer formed from the water repellent composition for automobile glass is required to have high dynamic water repellency (property of water droplets to be easily rolled, water drop removability), abrasion resistance and weather resistance.
  • a composition comprising a compound represented by the following formula (I) and a solvent (Patent Document 1).
  • Rf 1 is an organic group having a perfluoroalkyl group having 8 to 16 carbon atoms
  • R 1 is a hydrogen atom or an organic group having 1 to 16 carbon atoms
  • a is 1 or 2
  • the water-repellent layer formed from the water- and oil-repellent composition containing the fluorine-containing compound having a perfluoroalkyl group having 6 or less carbon atoms is compared with the water-repellent layer formed from the conventional water- and oil-repellent composition, Since the crystallinity based on the perfluoroalkyl group (that is, the property of packing between molecules) is inferior, water repellency, particularly dynamic water repellency is lowered.
  • Patent Document 3 A compound represented by the following formula (III) (Patent Document 3) and a mold release agent containing the compound (Patent Document 4).
  • n is an integer of 1 to 6
  • a is an integer of 1 to 4
  • b is an integer of 1 to 3
  • c is an integer of 1 to 3.
  • a water repellent layer is formed using a water / oil repellent composition containing a compound represented by the formula (II)
  • the adhesion to the substrate (particularly glass) is low, and the wear resistance and weather resistance are low.
  • the compound represented by the formula (III) is used as a release agent for a metal substrate, but is not suitable for other substrates (particularly glass).
  • the water repellent layer formed from the water / oil repellent composition containing the compound represented by the formula (IV) also has low adhesion to the substrate (particularly glass) and is inferior in wear resistance and weather resistance.
  • the present invention is capable of forming a water-repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance, and has a low environmental load and a coating composition and sufficient water repellency (
  • the present invention provides a substrate with a water-repellent layer having a dynamic water repellency), abrasion resistance and weather resistance, and having a low environmental load, and a method for producing the same.
  • R F Y—Si (R 1 ) 3-n (X) n
  • R F is a linear perfluoroalkyl group having carbon number p
  • Y is a straight-chain fluoroalkylene group having a carbon number q whose terminal on the R F side is —CH 2 — or a group in which an etheric oxygen atom is inserted between the carbon-carbon bonds of the fluoroalkylene group
  • p is an integer from 2 to 6
  • q is an integer of 4 or more
  • p + q is an integer of 10 or more
  • R 1 is a monovalent hydrocarbon group
  • X is a hydrolyzable group
  • n is an integer of 1 to 3.
  • R F A fluorine-containing compound represented by the following formula (11) or the following formula (12).
  • R F is a linear perfluoroalkyl group having carbon number p
  • p is an integer from 2 to 6
  • r is an integer of 1 or more
  • p + r + 4 is an integer of 10 or more
  • R 1 is a monovalent hydrocarbon group
  • X is a hydrolyzable group
  • n is an integer of 1 to 3.
  • R F is a linear perfluoroalkyl group having carbon number p
  • p is an integer from 2 to 6, - ⁇ (CH 2 CH 2 ) a ⁇ (CH 2 CF 2 ) b ⁇ (CF 2 CF 2 ) c ⁇ -is a-(CH 2 CH 2 ) -unit, b-(CH 2 CF 2 ) -units and c-(CF 2 CF 2 ) -units, wherein the R F end is a-(CH 2 CH 2 ) -unit or a-(CH 2 CF 2 ) -unit
  • the arrangement of the units is not limited, a is an integer of 0 to 10, b is an integer of 0 to 20, c is an integer from 0 to 10, a + b is an integer of 1 or more, b + c is an integer of 1 or more, p + 2a + 2b + 2c + 2 is an integer of 10 or more, R 1 is a monovalent hydrocarbon group, X
  • R F (CH 2 CF 2 ) b — (CF 2 CF 2 ) c —CH 2 CH 2 —Si (R 1 ) 3-n (X) n (12a).
  • R F is a linear perfluoroalkyl group having carbon number p
  • p is an integer from 2 to 6
  • — (CH 2 CF 2 ) b — (CF 2 CF 2 ) c — is the order in which b — (CH 2 CF 2 ) — units and c — (CF 2 CF 2 ) — units are listed.
  • b is an integer from 1 to 20
  • c is an integer from 1 to 10
  • p + 2b + 2c + 2 is an integer of 10 or more
  • R 1 is a monovalent hydrocarbon group
  • X is a hydrolyzable group
  • n is an integer of 1 to 3.
  • R F is a linear perfluoroalkyl group having carbon number p
  • p is an integer from 2 to 6
  • b is an integer from 1 to 20
  • p + 2b + 2 is an integer of 10 or more
  • R 1 is a monovalent hydrocarbon group
  • X is a hydrolyzable group
  • n is an integer of 1 to 3.
  • R F is a linear perfluoroalkyl group having carbon number p
  • p is an integer from 2 to 6
  • d is an integer of 1 to 10
  • p + 4d + 2 is an integer of 10 or more
  • R 1 is a monovalent hydrocarbon group
  • X is a hydrolyzable group
  • n is an integer of 1 to 3.
  • [4] The fluorine-containing compound according to any one of the above [1] to [3] and / or a partial hydrolysis-condensation product of the fluorine-containing compound, A coating composition comprising a solvent.
  • [5] The coating composition according to [4], wherein the total amount of the fluorine-containing compound and the partial hydrolysis-condensation product is 0.1 to 50% by mass with respect to the total mass of the coating composition.
  • [6] The coating composition according to [4] or [5], wherein the solvent is an organic solvent.
  • the coating composition according to any one of [4] to [6] which is a water / oil repellent composition.
  • [8] The coating composition according to any one of [4] to [6], which is used for forming a water-repellent or water- and oil-repellent layer on the substrate surface.
  • the coating composition according to any one of [4] to [8] is applied to the substrate surface, the solvent is removed by evaporation, and water repellency is obtained from the fluorine-containing compound and / or the partial hydrolysis-condensation product.
  • a surface treatment method for a substrate comprising forming a water- and oil-repellent layer on the substrate surface.
  • a method for producing a substrate with a water repellent layer wherein the coating composition according to any one of [4] to [8] is applied to the surface of the substrate to form a water repellent layer.
  • a substrate with a water-repellent layer comprising a substrate and a water-repellent layer formed on the surface of the substrate from the coating composition according to any one of [4] to [8].
  • the fluorine-containing compound of the present invention can form a water-repellent layer and a water- and oil-repellent layer having sufficient water repellency (particularly dynamic water repellency), water / oil repellency, abrasion resistance and weather resistance, and has a low environmental load.
  • the coating composition of the present invention can form a water-repellent layer and a water- and oil-repellent layer having sufficient water repellency (particularly dynamic water repellency), water / oil repellency, abrasion resistance and weather resistance, and has an environmental load. Few.
  • the substrate with a water repellent layer of the present invention has sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance, and has a low environmental load.
  • a substrate with a water-repellent layer having sufficient water repellency particularly dynamic water repellency
  • abrasion resistance and weather resistance and having a low environmental load.
  • a compound represented by the formula (1) is referred to as a compound (1).
  • the perfluoroalkyl group in the present specification refers to a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms.
  • the fluoroalkylene group refers to a group in which one or more hydrogen atoms of the alkylene group are substituted with fluorine atoms.
  • the perfluoroalkylene group refers to a group in which all hydrogen atoms of the alkylene group are substituted with fluorine atoms.
  • the fluorine-containing compound of the present invention is compound (1).
  • R F Y—Si (R 1 ) 3-n (X) n (1).
  • R F is a linear perfluoroalkyl group having p number of carbon atoms (where p is an integer of 2 to 6).
  • p is an integer of 2 to 6
  • p is 2 or more, the water and oil repellency is excellent. If p is 6 or less, there is little environmental load by the decomposition product of a fluorine-containing compound.
  • p is preferably 2, 4 or 6 from the viewpoint of availability of raw materials.
  • Y is a linear fluoroalkylene group having a carbon number q (where q is an integer of 4 or more) whose terminal on the R F side is —CH 2 —, or carbon of the fluoroalkylene group— It is a group in which an etheric oxygen atom is inserted between carbon bonds. In the case of the latter group, the number of etheric oxygen atoms is 1 or more.
  • Y is preferably a linear fluoroalkylene group.
  • q represents the number of carbon atoms of Y. If q is too large, the melting point of the fluorine-containing compound is increased, and the handleability is deteriorated.
  • the upper limit of q is preferably 28, more preferably 22, and particularly preferably 16.
  • the fluorine-containing compound of the present invention is characterized in that a linking group (Y) having a certain chain length exists between RF and Si, more preferably, the molecular chain length is long. is there.
  • P + q which is a number expressing the chain length of the molecule is 10 or more. When p + q is within this range, the crystallinity due to the R F —Y— group is maintained, and the resulting water-repellent layer has good dynamic water repellency.
  • p + q is preferably 10 to 30, more preferably 10 to 24, and particularly preferably 10 to 18.
  • the terminal on the R F side in Y is —CH 2 —.
  • a compound having an R F group having 8 or more carbon atoms is not generated as a decomposition product, so that the environmental load is small.
  • the end on the Si side in Y is —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 OCH 2 in view of weather resistance of the resulting water-repellent layer and ease of synthesis of the fluorine-containing compound.
  • CH 2 CH 2 — can be mentioned, and —CH 2 CH 2 — is particularly preferred.
  • R F and Y are linear. If R F and Y are linear, the R F —Y— group is linear, the crystallinity of the fluorine-containing compound is maintained, and the resulting water-repellent layer has good dynamic water repellency.
  • R 1 is a monovalent hydrocarbon group (excluding a hydrocarbon group having an R F group), and an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of availability of raw materials and handling properties.
  • R 1 may be the same group or different groups, and the same group is preferable from the viewpoint of availability.
  • X is a hydrolyzable group.
  • the hydrolyzable group is a group that can form Si—OH by hydrolysis of the Si—X group.
  • Examples of X include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, a halogen atom, and the like, and the stability of the fluorine-containing compound and the ease of hydrolysis. From the viewpoint of balance, an alkoxy group, an isocyanate group, and a halogen atom (particularly a chlorine atom) are preferable.
  • alkoxy group an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.
  • X may be the same group or different groups, and the same group is preferable from the viewpoint of availability.
  • N is an integer from 1 to 3. If n is 1 or more, the adhesiveness of the obtained water-repellent layer and a base material will become favorable. n is preferably 2 or 3, and particularly preferably 3, from the viewpoint of adhesion between the obtained water-repellent layer and the substrate.
  • the compound (1) from the viewpoint of water repellency (particularly dynamic water repellency), water / oil repellency, abrasion resistance and weather resistance of the resulting water repellent layer, and ease of synthesis of the fluorine-containing compound,
  • the compound (11) or the following compound (12) is preferable.
  • R F R F —CH 2 CH 2 — (CF 2 ) r —CH 2 CH 2 —Si (R 1 ) 3-n (X) n (11).
  • R F is an R F group having p carbon atoms
  • p is an integer from 2 to 6
  • r is an integer of 1 or more
  • p + r + 4 (p + r + 4 corresponds to p + q in formula (1)) is an integer of 10 or more
  • R 1 is a monovalent hydrocarbon group
  • X is a hydrolyzable group
  • n is an integer of 1 to 3.
  • R F , p, p + r + 4, R 1 , X and n are the same as those of the compound (1).
  • r is too large, the melting point of the fluorine-containing compound is increased, and the handleability is deteriorated.
  • the preferable upper limit of r is 24, 18 is more preferable, and 12 is particularly preferable.
  • p + q + 4 is within this range, the crystallinity of the fluorine-containing compound is maintained by the R F —CH 2 CH 2 — (CF 2 ) r —CH 2 CH 2 — group, and the resulting water-repellent layer has a dynamic water repellency. It becomes good.
  • p + r + 4 is preferably 10 to 30, more preferably 10 to 24, and still more preferably 10 to 18.
  • Preferable specific examples of compound (11) include the following compounds. CF 3 CF 2 —CH 2 CH 2 — (CF 2 ) 6 —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 —CH 2 CH 2 — (CF 2 ) 6 —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 5 —CH 2 CH 2 — (CF 2 ) 6 —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 —CH 2 CH 2 — (CF 2 ) 6 —CH 2 CH 2 —Si (OCH 3 ) 3 , CF 3 (CF 2 ) 3 —CH 2 CH 2 — (CF 2 ) 6 —CH 2 CH 2 —Si (CH 3 ) (OCH 3 ) 2 , CF 3 (CF 2 ) 3 —
  • R F is an R F group having p carbon atoms
  • p is an integer from 2 to 6, - ⁇ (CH 2 CH 2 ) a ⁇ (CH 2 CF 2 ) b ⁇ (CF 2 CF 2 ) c ⁇ -is a-(CH 2 CH 2 ) -unit, b-(CH 2 CF 2 ) -units and c-(CF 2 CF 2 ) -units, wherein the R F end is a-(CH 2 CH 2 ) -unit or a-(CH 2 CF 2 ) -unit
  • a is an integer of 0 to 10
  • b is an integer of 0 to 20
  • c is an integer from 0 to 10
  • a + b is an integer of 1 or more
  • b + c is an integer of 1 or more
  • p + 2a + 2b + 2c + 2 (p + 2a + 2b + 2c + 2 corresponds to p + q in formula (1)) is an
  • R F , p, p + 2a + 2b + 2c + 2, R 1 , X and n are the same as those of the compound (1).
  • p + 2a + 2b + 2c + 2 in the compound (12) is 10 or more, it is contained by R F — ⁇ (CH 2 CH 2 ) a ⁇ (CH 2 CF 2 ) b ⁇ (CF 2 CF 2 ) c ⁇ —CH 2 CH 2 — group.
  • the crystallinity of the fluorine compound is maintained, and the resulting water-repellent layer has good dynamic water repellency.
  • p + 2a + 2b + 2c + 2 becomes too large, the melting point of the fluorine-containing compound becomes high, and the handleability deteriorates.
  • p + 2a + 2b + 2c + 2 is preferably 10 to 30, more preferably 10 to 24, and particularly preferably 10 to 18.
  • a + b + c is preferably 1 to 13, more preferably 1 to 10, and particularly preferably 1 to 7.
  • a is preferably 0 to 6, particularly preferably 0 to 3.
  • b is preferably 0 to 13, particularly preferably 0 to 4.
  • c is preferably 0 to 12, particularly preferably 0 to 6.
  • the compound (12) is preferably the compound (12a), the compound (12b), or the compound (12c) from the viewpoint of easy synthesis of the fluorine-containing compound.
  • R F (CH 2 CF 2 ) b — (CF 2 CF 2 ) c —CH 2 CH 2 —Si (R 1 ) 3-n (X) n (12a).
  • R F is an R F group having p carbon atoms
  • p is an integer from 2 to 6
  • b is an integer from 1 to 20
  • c is an integer from 1 to 10
  • p + 2b + 2c + 2 (p + 2b + 2c + 2 corresponds to p + q in formula (1)) is an integer of 10 or more
  • R 1 is a monovalent hydrocarbon group
  • X is a hydrolyzable group
  • n is an integer of 1 to 3.
  • R F , p, p + 2b + 2c + 2, R 1 , X and n are the same as those of the compound (12).
  • the crystallinity of the fluorine-containing compound is maintained by the R F — (CH 2 CF 2 ) b — (CF 2 CF 2 ) c —CH 2 CH 2 — group.
  • the resulting water-repellent layer has good dynamic water repellency.
  • b is preferably from 1 to 12, particularly preferably from 1 to 6.
  • c is preferably from 1 to 12, particularly preferably from 1 to 6.
  • b + c is preferably 2 to 13, more preferably 2 to 10, and particularly preferably 2 to 7.
  • p + 2b + 2c + 2 is preferably 10 to 30, more preferably 10 to 24, and particularly preferably 10 to 18.
  • the compound (12a) include the following compounds. CF 3 CF 2 —CH 2 CF 2 — (CF 2 CF 2 ) 2 —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 —CH 2 CF 2 —CF 2 CF 2 —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 —CH 2 CF 2 — (CF 2 CF 2 ) 3 —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 — (CH 2 CF 2 ) 3 —CF 2 CF 2 —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 — (CH 2 CF 2 ) 3 —CF 2 CF 2 —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3
  • R F (CH 2 CF 2 ) b —CH 2 CH 2 —Si (R 1 ) 3-n (X) n (12b).
  • R F is an R F group having p carbon atoms
  • p is an integer from 2 to 6
  • b is an integer from 1 to 20
  • p + 2b + 2 (p + 2b + 2 corresponds to p + q in formula (1)) is an integer of 10 or more
  • R 1 is a monovalent hydrocarbon group
  • X is a hydrolyzable group
  • n is an integer of 1 to 3.
  • R F , p, p + 2b + 2, R 1 , X and n are the same as those of the compound (12).
  • R F — ⁇ (CH 2 CH 2 ) — (CF 2 CF 2 ) ⁇ d —CH 2 CH 2 —Si (R 1 ) 3-n (X) n (12c).
  • R F is an R F group having p carbon atoms
  • p is an integer from 2 to 6
  • d is an integer of 1 to 10
  • p + 4d + 2 (p + 4d + 2 corresponds to p + q in formula (1)) is an integer of 10 or more
  • R 1 is a monovalent hydrocarbon group
  • X is a hydrolyzable group
  • n is an integer of 1 to 3.
  • R F , p, p + 4d + 2, R 1 , X and n are the same as those of the compound (12).
  • the crystallinity of the fluorine-containing compound is maintained by the R F — ⁇ CH 2 CH 2 CF 2 CF 2 ⁇ d —CH 2 CH 2 — group, and the obtained repellent property is obtained.
  • the dynamic water repellency of the water layer is improved.
  • d is preferably 1 to 7, more preferably 1 to 5, and particularly preferably 1 to 4.
  • p + 4d + 2 is preferably 10 to 32, more preferably 10 to 26, and particularly preferably 10 to 20.
  • Preferable specific examples of the compound (12c) include the following compounds.
  • CF 3 CF 2 — ⁇ (CH 2 CH 2 ) — (CF 2 CF 2 ) ⁇ 3 —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 — ⁇ (CH 2 CH 2 ) — (CF 2 CF 2 ) ⁇ — CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 — ⁇ (CH 2 CH 2 ) — (CF 2 CF 2 ) ⁇ 3 —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 5 — ⁇ (CH 2 CH 2 ) — (CF 2 CF 2 ) ⁇ — CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 — ⁇ (CH 2 CH 2 ) — (CF 2 CF 2 ) ⁇ — CH 2 CH 2 —Si (OCH 3 ) 3 , CF 3 (CF 2 ) 3 — ⁇ (CH 2 CH 2 )
  • Examples of compounds other than the compounds (12a) to (12c) include the following compounds. CF 3 (CF 2 ) 3 — (CH 2 CH 2 ) — (CF 2 CF 2 ) — (CH 2 CF 2 ) —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 — (CH 2 CF 2 ) — (CH 2 CH 2 ) — (CF 2 CF 2 ) —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 — (CH 2 CF 2 ) — (CF 2 CF 2 ) — (CH 2 CH 2 ) —CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 — (CH 2 CH 2 ) 2 — (CF 2 CF 2 ) — (CH 2 CH 2 —SiCl 3 , CF 3 (CF 2 ) 3 — (CH 2 CH 2 ) 2 — (CF 2 CF 2 ) —
  • compound (4) is obtained by addition reaction of perfluoroalkyl iodide (compound (2)) with ⁇ , ⁇ -divinylperfluoroalkane (compound (3)), and then compound (4) is reduced with a reducing agent (for example, In this method, compound (5) is obtained by reduction with tributyltin hydride, tris (trimethylsilyl) silane, etc., and then compound (11) is obtained by hydrosilylation reaction between compound (5) and compound (6). (However, the meanings in the following formula are the same as those in the compound (11)).
  • the production method is a method for producing the compound (1) when both ends of Y are —CH 2 CH 2 —.
  • the same reaction is performed using another compound having a different-(CF 2 ) r -moiety in formula (3) instead of the compound represented by formula (3). Can be manufactured.
  • compound (2) is reacted with a compound arbitrarily selected from compounds (7a) to (7c) to obtain compound (8).
  • Examples of the subsequent reaction include the following method A and method B.
  • Method A Compound (9) is obtained by addition reaction of compound (8) and ethylene (compound (7a)), and then compound (10) is obtained by dehydroiodination of compound (9) in the presence of a base.
  • the compound (12) is obtained by hydrosilylation reaction of the compound (10) and the compound (6).
  • R F — ⁇ (CH 2 CH 2 ) a ⁇ (CH 2 CF 2 ) b ⁇ (CF 2 CF 2 ) c ⁇ —CH ⁇ CH 2 (10).
  • Compound (14) is obtained by addition reaction of compound (8) and vinylsilane compound (compound (13)), and then compound (14) is reduced to a reducing agent (for example, tributyltin hydride, tris (trimethylsilyl) silane, or the like.
  • a reducing agent for example, tributyltin hydride, tris (trimethylsilyl) silane, or the like.
  • Either method A or method B may be adopted.
  • the dehydrofluorination reaction proceeds depending on the type of base of the dehydroiodination reaction and the reaction conditions. May change to —CF ⁇ CH—CF 2 — or —CF 2 —CH ⁇ CF—. Such changes can adversely affect the weather resistance of the product. Therefore, the method B is preferably adopted for the compound (12) having a —CF 2 —CH 2 —CF 2 — structure. Even when the compound (8) contains a —CF 2 —CH 2 —CH 2 — structure, the structure can be changed to a —CF ⁇ CH—CH 2 — structure. However, since this change is easy to avoid depending on the type of base and reaction conditions, Method A and Method B can be used.
  • CF 2 CF 2 (7c), R F — (CH 2 CF 2 ) b — (CF 2 CF 2 ) c —I (8a).
  • CH 2 CH-Si (R 1 ) 3-n (X) n (13), R F — (CH 2 CF 2 ) b — (CF 2 CF 2 ) c —CH 2 CHI—Si (R 1 ) 3-n (X) n (14a).
  • CH 2 CH-Si (R 1 ) 3-n (X) n (13), R F — (CH 2 CF 2 ) b —CH 2 CHI—Si (R 1 ) 3-n (X) n (14b). R F — (CH 2 CF 2 ) b —CH 2 CH 2 —Si (R 1 ) 3-n (X) n (12b).
  • compound (10c) is obtained by dehydroiodination of compound (9c) in the presence of a base, and then compound (12c) is obtained by hydrosilylation reaction between compound (10c) and compound (6).
  • Method (however, the symbols in the formulas have the same meaning as in compound (12c)).
  • R F -I (2), CH 2 CH 2 (7a), R F —CH 2 CH 2 —I (8c).
  • CF 2 CF 2 (7c), R F — ⁇ CH 2 CH 2 CF 2 CF 2 ⁇ d —CH 2 CH 2 —I (9c).
  • the fluorine-containing compound of the present invention obtained by the above-described production method may be used after removing impurities by a method such as purification by a known method (distillation or the like), or may be used as it is. Moreover, when it obtains as a mixture of the fluorine-containing compound of this invention, each may be used after isolate
  • the fluorine-containing compound of the present invention can be used as a water / oil repellent, a mold release agent, an antifouling agent, a fingerprint removal performance imparting agent, an easy cleaning imparting agent, etc., and an article (window glass etc.) for transportation equipment (automobile etc.) It is suitable as a water repellent.
  • R F has 2 or more carbon atoms
  • the R F —Y— group has 10 or more carbon atoms
  • the R F —Y— group is linear.
  • the crystallinity of the fluorine-containing compound is maintained by the F— Y— group, and the resulting water-repellent layer has good water repellency (particularly dynamic water repellency) and water / oil repellency.
  • the resulting water-repellent layer has high adhesion to the substrate (particularly glass), and the resulting water-repellent layer The layer has good wear resistance and weather resistance.
  • the number of carbon atoms in R F is 6 or less and the terminal on the R F side in Y is —CH 2 —, the environmental load due to the decomposition product of the fluorine-containing compound is small.
  • the coating composition of the present invention contains the fluorine-containing compound of the present invention and / or a partial hydrolysis-condensation product of the fluorine-containing compound and a solvent.
  • fluorine-containing compounds may be used singly or in a case where a hydrolytic condensation reaction is performed, or one kind or two or more kinds may be used.
  • Partial hydrolysis condensate As a generation mechanism of the partially hydrolyzed condensate, a part or all of the hydrolyzable silyl group (Si—X group) of the fluorine-containing compound is hydrolyzed to form a silanol group (Si—OH group), It is considered that silanol groups are produced by dehydration condensation between each other to form oligomers (multimers).
  • the hydrolysis condensation reaction is preferably carried out in a solvent in the presence of a catalyst (an acid catalyst, an alkali catalyst, etc.) and water.
  • the partially hydrolyzed condensate may contain an unreacted fluorine-containing compound. However, if the hydrolysis-condensation reaction proceeds too much, it becomes difficult to dissolve in a solvent, and therefore a certain degree of condensation is required.
  • the hydrolysis condensation reaction may be promoted by heating. However, if the reaction proceeds too much, the degree of condensation may increase too much and a solvent-insoluble product may be produced. As long as an appropriate amount of catalyst is present, it is preferable to react at room temperature. You may use the solution of the obtained partial hydrolysis-condensation product as a coating composition of this invention as it is.
  • the solvent used for the hydrolysis condensation is preferably a solvent that dissolves the fluorine-containing compound of the present invention and its partial hydrolysis-condensation product, and an organic solvent is particularly preferable.
  • Organic solvents include alcohols, ethers, ketones, esters, aromatic hydrocarbons, paraffinic hydrocarbons, fluorine-containing organic solvents (hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers, polyfluoroalcohols, etc.)
  • organic solvents other than the fluorine-containing organic solvent are preferable.
  • heptane and butyl acetate are preferable in terms of cost and handling.
  • An organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • Examples of the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like.
  • Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, ammonia and the like.
  • Hydrolysis condensation reaction may be carried out by (1) dissolving the fluorine-containing compound of the present invention in an organic solvent and adding the catalyst and water separately or an aqueous solution of the catalyst, or (2) the fluorine-containing compound of the present invention. It is preferably carried out by a method of adding a catalyst or an aqueous solution of the catalyst to a solution dissolved or mixed in an organic solvent containing water.
  • the amount of the catalyst used for the production of the partial hydrolysis-condensation product is preferably 0.0001 to 1 part by weight, particularly preferably 0.001 to 0.1 part by weight, based on 1 part by weight of the fluorine-containing compound. When the amount of the catalyst is within this range, the hydrolysis effect is sufficiently exhibited and the composition is excellent in stability.
  • the amount of water used for the production of the partial hydrolysis-condensation product is preferably 0.00001 to 0.1 parts by mass, particularly preferably 0.0001 to 0.01 parts by mass with respect to 1 part by mass of the fluorine-containing compound. When the amount of water is within this range, the hydrolysis effect is sufficiently exhibited, and the composition is excellent in stability.
  • the coating composition of the present invention preferably contains a solvent from the viewpoints of economy, workability, ease of control of the thickness of the resulting water-repellent layer, and the like.
  • a solvent the organic solvent mentioned as a solvent used for manufacture of a partial hydrolysis-condensation product is preferable.
  • the organic solvent may be added separately, and when it contains a partially hydrolyzed condensate, it may contain the solvent used for the production of the partially hydrolyzed condensate.
  • the solvent used for the production of the partially hydrolyzed condensate may be used.
  • the coating composition of the present invention may contain a catalyst in order to promote hydrolysis and condensation of the fluorine-containing compound.
  • a catalyst an acid catalyst is preferable as the catalyst.
  • a water-repellent layer with good water droplet removal and durability can be formed.
  • the coating composition of the present invention may contain an additive as an optional component depending on the purpose within a range not impairing the effects of the present invention.
  • Additives include non-fluorinated water repellent materials (one-end reactive polydimethylsiloxane, both-end reactive polydimethylsiloxane, etc.), ultrafine metal oxide particles (silica, alumina, zirconia, titania, etc.), coloring materials (Dyes, pigments, etc.), antifouling materials, curing catalysts, various resins and the like.
  • the additive is preferably selected in consideration of the reactivity or compatibility with essential components.
  • the total amount of the fluorine-containing compound and the partial hydrolysis-condensation product of the present invention is preferably from 0.1 to 50% by mass, more preferably from 0.1 to 20% by mass, based on the total mass of the coating composition. 15% by mass is particularly preferred. If the total amount of the fluorine-containing compound and the partially hydrolyzed condensate is not less than the lower limit of the above range, unevenness is unlikely to occur in the resulting water-repellent layer. If it is below the upper limit of the said range, it is excellent in storage stability.
  • the amount of the additive is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the solid content of the coating composition (a component excluding volatile components such as an organic solvent). Excessive addition of the functional additive to the coating composition may cause a decrease in performance such as water droplet removability of the resulting water-repellent layer.
  • the coating composition of the present invention is applied to the surface of the substrate, the solvent is removed by evaporation, and the water-repellent or water-repellent and water-repellent properties are removed from the fluorine-containing compound and / or partially hydrolyzed condensate.
  • An oily layer is formed on the substrate surface.
  • Fluorine-containing compounds and partially hydrolyzed condensates include hydrolysis reaction from hydrolyzable groups to silanol groups, dehydration condensation reaction between silanol groups, reaction of functional groups on the substrate surface with silanol groups and hydrolyzable groups, By reacting with each other and bonding with each other, and in some cases, reacting and bonding with the surface of the base material, a layer of a dehydration condensation reaction product is formed on the surface of the base material. Since the layer formed from the coating composition of the present invention has water repellency and water / oil repellency, the coating composition of the present invention is used for applications requiring these characteristics.
  • the coating composition of the present invention is used to form a water-repellent or water- and oil-repellent layer on the substrate surface.
  • it can be used as a water repellent composition, a water / oil repellent composition, a release agent composition, an antifouling agent composition, a fingerprint removal performance imparting agent composition, an easy cleaning imparting agent composition, and the like.
  • the material for the substrate include metals, plastics, glass, ceramics, and combinations thereof (composite materials, laminated materials, etc.).
  • the coating composition of the present invention described above contains the fluorine-containing compound of the present invention and / or a partially hydrolyzed condensate thereof, sufficient water repellency (particularly dynamic water repellency), water repellency and oil repellency.
  • a water-repellent layer and a water- and oil-repellent layer having wear resistance and weather resistance can be formed, and the environmental load is small.
  • the coating composition of the present invention is particularly preferably used for forming a water repellent layer on a substrate.
  • the present invention is also a substrate with a water repellent layer and a method for producing the same.
  • the present invention is a transportation device equipped with a substrate with a water repellent layer.
  • it is an automobile in which a substrate with a water repellent layer is mounted as a window glass of an automobile or the like.
  • the substrate with a water repellent layer of the present invention has a substrate and a water repellent layer formed on the surface of the substrate from the coating composition.
  • the water repellent layer is preferably present in the outermost layer.
  • the surface of the substrate and the water repellent layer may be in direct contact or may be in contact with each other through another layer. Other layers will be described later.
  • the water repellent layer is provided on at least a part of the surface of the base material.
  • the water repellent layer is provided on at least one side of the base material.
  • Base material A base material will not be specifically limited if it is a base material with which the provision of water repellency is calculated
  • Examples of the material for the substrate include metals, plastics, glass, ceramics, and combinations thereof (composite materials, laminated materials, etc.).
  • a translucent substrate that transmits visible light is preferable from the viewpoint of transparency.
  • the water-repellent layer formed using the coating composition of the present invention has high dynamic water repellency, abrasion resistance, and weather resistance, it is a window glass for transportation equipment (trains, automobiles, ships, aircrafts, etc.) Is particularly preferred.
  • the glass include soda lime glass, borosilicate glass, non-alkali glass, and quartz glass, and soda lime glass is particularly preferable.
  • the substrate may be a flat plate, or the entire surface or a part thereof may have a curvature.
  • the thickness of the substrate may be appropriately selected depending on the use of the substrate with a water repellent layer, and is usually 1 to 10 mm.
  • the surface of the substrate may be acid-treated (treated with diluted hydrofluoric acid, sulfuric acid, hydrochloric acid, etc.), alkali-treated (treated with an aqueous sodium hydroxide solution), discharge treatment (plasma irradiation) , Corona irradiation, electron beam irradiation, etc.) may be used.
  • the base material may be provided with various films formed on its surface by a vapor deposition film, a sputtered film, a wet method or the like. When the base material is soda lime glass, it is preferable in terms of durability to provide a film for preventing elution of sodium ions.
  • the water repellent layer is formed so as to cover at least a part of the surface of the substrate.
  • the water repellent layer may be formed directly on the surface of the base material, or may be formed on the surface of another layer formed on the surface of the base material. In any case, the water repellent layer is formed on the outermost layer of the substrate with a water repellent layer of the present invention.
  • the base material is glass manufactured by a float process, it is preferable in terms of durability to provide a water-repellent layer on the top surface with a small amount of tin on the surface.
  • the thickness of the water-repellent layer is not particularly limited as long as it is compatible with dynamic water repellency (removability of water droplets) and durability (abrasion resistance, weather resistance, etc.), preferably 2 to 30 nm. Is particularly preferred.
  • the thickness of the water repellent layer can be appropriately controlled depending on the concentration of the coating composition, application conditions, heating conditions, and the like.
  • the other layer is preferably an intermediate layer mainly composed of silica.
  • the silica intermediate layer is formed on the glass plate surface on which at least the water repellent layer is provided.
  • middle layer is a layer specifically formed using the composition for intermediate
  • the silica precursor include a compound selected from the compound (20), a partially hydrolyzed condensate thereof, and perhydropolysilazane.
  • X 1 to X 4 are each a hydrolyzable group, preferably a halogen atom, an alkoxy group or an isocyanate group.
  • X 1 to X 4 are each preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms or an isocyanate group, and more preferably all of X 1 to X 4 are the same.
  • the partial hydrolysis-condensation product of a compound (20) can be obtained by the method similar to having demonstrated in manufacture of the partial hydrolysis-condensation product of the fluorine-containing compound of this invention.
  • Commercially available products may be used as the compound (20) and its partially hydrolyzed condensate.
  • a compound (20) may be used individually by 1 type, and may use 2 or more types together.
  • Perhydropolysilazane is a linear or cyclic oligomer having a structure represented by —SiH 2 —NH—SiH 2 —.
  • the number of silicon atoms per molecule of perhydropolysilazane is preferably 2 to 500.
  • a commercially available product may be used as perhydropolysilazane.
  • the composition for forming an intermediate layer may contain a hydrolysis cocondensate of the compound (20) and / or a partial hydrolysis condensate thereof and the fluorine-containing compound of the present invention and / or a partial hydrolysis condensate thereof. (The compound (20) and / or the fluorine-containing compound of the present invention may further be included if necessary).
  • the composition for forming an intermediate layer usually contains an organic solvent from the viewpoints of economy, workability, ease of controlling the thickness of the intermediate layer, and the like. As an organic solvent, the organic solvent mentioned as the organic solvent used for the composition for coating is preferable.
  • the ratio of the silica precursor in the intermediate layer forming composition (100% by mass) can be the same as that in the coating composition.
  • middle layer is not specifically limited, Since damage will become conspicuous if it is too thick, 50 nm or less is preferable.
  • the lower limit of the thickness of the intermediate layer is the thickness of the monomolecular layer.
  • the thickness of the intermediate layer can be appropriately controlled depending on the concentration of the intermediate layer forming composition, coating conditions, heating conditions, and the like.
  • the total thickness of the water repellent layer and other layers (intermediate layer, etc.) is to maintain the function of the water repellent layer, that is, dynamic water repellency (removability of water droplets) and durability (wear resistance, weather resistance, etc.) 2 to 100 nm is preferable and 5 to 20 nm is particularly preferable from the viewpoints of both compatibility and economic efficiency.
  • the base material with a water-repellent layer of the present invention is suitably used for applications for articles for transportation equipment.
  • the transportation equipment article include bodies, window glass (front glass, side glass, rear glass), mirrors, bumpers and the like in transportation equipment (trains, automobiles, ships, aircrafts, etc.).
  • the article for transportation equipment comprising the substrate with a water-repellent layer according to the present invention has little water droplet adhesion to the surface, and the adhered water droplets are repelled promptly. .
  • the attached water droplets move rapidly on the surface and do not accumulate as water droplets. For this reason, the bad influence which a water drop induces can be excluded.
  • the water-repellent layer is also excellent in abrasion resistance and weather resistance, for example, it is possible to maintain the water droplet removability even in long-term use under various use conditions including outdoor use as an article for transport equipment.
  • the article for transportation equipment comprising the substrate with a water-repellent layer of the present invention is particularly easy in securing the field of view due to the splashing of water droplets, especially in applications in various fields of view such as various types of window glass. Safety can be improved. Further, it is difficult to freeze even in an environment where water droplets freeze, and even if it freezes, thawing is extremely fast. Furthermore, since there is almost no adhesion of water droplets, the number of cleaning operations can be reduced, and the cleaning operation can be easily performed.
  • the method for producing a substrate with a water-repellent layer according to the present invention comprises applying the coating composition of the present invention to the surface of a substrate or the surface of another layer on which the surface of the substrate is formed and curing to repel the surface. This is a method of forming an aqueous layer.
  • Application methods include brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, hand coating, roll coating method, casting method, dip coating method (dipping method), spin coating method, water casting method, Examples thereof include a die coating method, a Langmuir project method, and a vacuum deposition method. Squeegee application is preferred because there is no factor that impairs the utilization efficiency of the material, such as scattering of the material, and it is difficult to waste the material.
  • the curing method include a method of curing in air or nitrogen gas after preliminary drying as necessary. By pre-drying, the solvent of the coating composition can be easily removed.
  • the curing conditions are appropriately controlled depending on the type and concentration of the coating composition.
  • Preferred curing conditions include temperature: 20 to 50 ° C. and humidity: 50 to 90% RH.
  • the curing time depends on the type, concentration, curing conditions, etc. of the coating composition, but is generally preferably 1 to 72 hours.
  • an excess component may be generated on the surface of the water-repellent layer and the appearance quality may be impaired.However, the excess component may be removed by wiping the surface of the water-repellent layer with a solvent, Remove and adjust the appearance.
  • heat treatment may be performed.
  • the heating temperature is usually 50 to 300 ° C.
  • the heating time is usually 1 to 120 minutes.
  • the substrate with a water-repellent layer of the present invention described above has a water-repellent layer formed using the coating composition of the present invention, so that it has sufficient water repellency (particularly dynamic water repellency) and resistance to water. Abrasion and weather resistance.
  • the coating composition of the present invention is applied to the surface of the substrate or the surface of another layer on which the surface of the substrate is formed. Therefore, a substrate with a water-repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance and less environmental load can be produced.
  • Example 1 to 10 and 14 to 18 are examples
  • Examples 11 and 19 are comparative examples
  • Examples 12 and 20 are reference examples
  • Example 13 is a preparation example.
  • a reactor equipped with a stirrer and a dropping funnel (internal volume 100 mL, made of glass) was charged with 50.0 g of the mixture containing the compound (4-1) and stirred, and the internal temperature of the reactor was adjusted in an oil bath. Heated to 80 ° C. Then, 16.6 g of tributyltin hydride was added dropwise so that the internal temperature of the reactor became 80 to 85 ° C., and the mixture was further stirred for 2 hours.
  • the obtained reaction crude liquid was subjected to simple distillation (boiling point / 5 hPa to 100 ° C./5 hPa). Were mixed and the solid was filtered off.
  • Example 2 40.0 g of the compound (2-2) and 95.3 g of the compound (3-1) were added to a sealed pressure resistant reactor (100 mL, manufactured by SUS) and stirred. The reactor was then placed in a 200 ° C. oil bath and stirred for 20 hours. The raw material was removed from the obtained reaction crude liquid by simple distillation to obtain 90.1 g of a mixture containing the compound (4-2). The purity by GC (gas chromatography) was 25%, and the yield was 31%.
  • a reactor equipped with a stirrer and a dropping funnel (internal volume: 100 mL, made of glass) was charged with 90.1 g of the mixture containing the compound (4-2) and stirred, and the internal temperature of the reactor was adjusted with an oil bath. Heated to 80 ° C. Next, 16.4 g of tributyltin hydride was added dropwise so that the internal temperature of the reactor became 80 to 85 ° C., and the mixture was further stirred for 2 hours.
  • reaction crude liquid was subjected to simple distillation (boiling point / 3 hPa to 104 ° C./3 hPa), and the distillate was mixed with 0.5 g of activated carbon and 30 mL of AC-6000, and the solid was separated by filtration. Subsequently, the solvent of the filtrate was distilled off to obtain 14.2 g of the compound (5-2) (colorless transparent liquid). The yield was 62%.
  • Example 3 700 g of compound (2-1) and 4.38 g of di (t-butyl) peroxide are charged into a pressure-resistant reactor (1 L, manufactured by SUS), and the internal temperature of the reactor becomes 115 ° C. in an oil bath. Heated. Subsequently, the compound (7b) was continuously introduced so that the internal pressure of the reactor became 0.7 MPa, and when the introduction amount reached 260 g, the introduction of the compound (7b) was stopped. Thereafter, the reaction was stopped when the internal pressure of the reactor reached 0 MPa.
  • the Dim funnel of the reactor containing the reaction crude liquid was changed to a dropping funnel, and heated in an oil bath so that the internal temperature of the reactor became 80 ° C.
  • 8.98 g of tributyltin hydride was added dropwise so that the internal temperature of the reactor became 80 to 85 ° C., and the mixture was further stirred for 2 hours.
  • the obtained reaction crude liquid was subjected to simple distillation (boiling point / 5 hPa to 70 ° C./5 hPa) to obtain 6.5 g of compound (12a-1) (colorless transparent liquid).
  • the yield was 83%.
  • the Dim funnel of the reactor containing the reaction crude liquid was changed to a dropping funnel, and heated in an oil bath so that the internal temperature of the reactor became 80 ° C.
  • 6.69 g of tributyltin hydride was added dropwise so that the internal temperature of the reactor became 80 to 85 ° C., and the mixture was further stirred for 2 hours.
  • the obtained reaction crude liquid was subjected to simple distillation (boiling point / 5 hPa to 93 ° C./5 hPa) to obtain 13.3 g of compound (12a-2) (colorless transparent liquid).
  • the yield was 96%.
  • Example 5 In a reactor equipped with a stirrer and a Dimroth (50 mL, made of glass), 20.0 g of the compound (8b-3) obtained in Example 3 above, 9.00 g of the compound (13-2), N, N′— 0.18 g of azobisisobutyronitrile and 20 g of AC-6000 were added, and the reactor was heated so that the internal temperature of the reactor became 70 ° C. After stirring for 12 hours, the unreacted raw material and AC-6000 were distilled off to obtain 26.1 g of a mixture containing the compound (14b-1). The purity by GC was 80%, and the yield was 82%. CF 3 (CF 2 ) 3 — (CH 2 CF 2 ) 3 —CH 2 CHI—Si (OCH 3 ) 3 (14b-1).
  • the Dim funnel of the reactor containing the reaction crude liquid was changed to a dropping funnel, and heated in an oil bath so that the internal temperature of the reactor became 80 ° C.
  • 11.4 g of tributyltin hydride was added dropwise so that the internal temperature of the reactor became 80 to 85 ° C., and the mixture was further stirred for 2 hours.
  • the obtained reaction crude liquid was subjected to simple distillation (boiling point / 5 hPa to 96 ° C./5 hPa) to obtain 13.9 g of compound (12b-1) (colorless transparent liquid).
  • the yield was 64%.
  • Example 6 In a glass container in which a stirrer is set, 2.22 g of heptane (manufactured by Junsei Kagaku), 2.22 g of butyl acetate (manufactured by Junsei Kagaku), and 0.57 g of compound (11-1) are placed at 25 ° C. For 30 minutes to obtain a coating composition (J-1).
  • Example 7 In a glass container in which a stirrer is set, 3.48 g of heptane, 0.87 g of butyl acetate, and 0.65 g of compound (11-2) are added, and stirred at 25 ° C. for 30 minutes. J-2) was obtained.
  • Example 8 In a glass container in which a stirrer is set, 0.91 g of heptane, 0.91 g of butyl acetate, and 0.18 g of compound (12a-1) are added and stirred at 25 ° C. for 30 minutes. J-3) was obtained.
  • Example 9 In a glass container in which a stirrer is set, 4.33 g of isopropanol, 0.13 g of 1.0 mass% nitric acid aqueous solution and 0.54 g of compound (12a-2) are placed, and stirred at 25 ° C. for 3 hours. A coating composition (J-4) was obtained.
  • Example 10 In a glass container in which a stirrer was set, 4.37 g of isopropanol, 0.13 g of 1.0 mass% nitric acid aqueous solution and 0.50 g of compound (12b-1) were placed, and stirred at 25 ° C. for 3 hours. A coating composition (J-5) was obtained.
  • Example 11 In a glass container in which a stirrer is set, 2.31 g of heptane, 2.31 g of butyl acetate and 0.39 g of compound (21) (manufactured by Gerest) are stirred at 25 ° C. for 30 minutes for coating. A composition (J-6) was obtained. CF 3 (CF 2 ) 5 —CH 2 CH 2 —SiCl 3 (21).
  • Example 12 In a glass container in which a stirrer is set, 3.63 g of heptane, 0.91 g of butyl acetate and 0.47 g of compound (22) (manufactured by Gerest) are stirred for 30 minutes at 25 ° C. A composition (J-7) was obtained. CF 3 (CF 2 ) 7 —CH 2 CH 2 —SiCl 3 (22).
  • the water drop removability was evaluated by the values of water contact angle (CA) and water drop angle (SA) measured by the following method. First, the initial values of the water contact angle and the water falling angle were measured before the following tests (abrasion resistance, alkali resistance, weather resistance), and the water contact angle and the water falling angle were also measured after each test. If the water contact angle is 90 ° or more and the water falling angle is 20 ° or less, it can be said that the water droplet removal property can withstand practical use.
  • CA water contact angle
  • SA water drop angle
  • the contact angle of a water droplet having a diameter of 1 mm placed on the surface of the water-repellent layer of the substrate with the water-repellent layer was measured using CA-X150 (manufactured by Kyowa Interface Science Co., Ltd.). Measurement was performed at five different locations on the surface of the water repellent layer, and the average value was calculated.
  • the substrate with a water repellent layer was immersed in an aqueous sodium hydroxide solution having a pH of 11 for 2 hours. After the substrate was washed with water and dried, the water contact angle and the water falling angle were measured by the above methods.
  • Example 14 As a substrate, a clean soda lime glass plate (water contact angle: 5 °, 300 mm ⁇ 300 mm ⁇ thickness 3 mm) was prepared by polishing and cleaning the surface with cerium oxide. On the surface of the glass plate, 2 g of the intermediate layer forming composition was applied by a squeegee coating method and held at 25 ° C. for 1 minute to form an intermediate layer. Next, 2 g of the coating composition (J-1) was applied to the surface of the intermediate layer by a squeegee coating method, and kept in a constant temperature and humidity chamber set at 50 ° C. and 60% RH for 48 hours for water repellency. A layer was formed to obtain a substrate with a water-repellent layer. The evaluation results are shown in Table 1.
  • Example 15 to 20 A substrate with a water repellent layer was obtained in the same manner as in Example 14 except that the coating composition (J-1) was changed to coating compositions (J-2) to (J-7). The evaluation results are shown in Table 1.
  • the base material with a water-repellent layer of Example 20 having a water-repellent layer formed using the coating composition of Reference Example obtained in Example 12 had the same performance as in Examples 14-18.
  • the coating composition containing the fluorine-containing compound of the present invention it is possible to impart excellent water droplet removal properties to the substrate, and furthermore, the load applied to the environment while having sufficient durability. Is low.
  • the fluorine-containing compound of the present invention is useful as a material for forming a water-repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance, and having a low environmental load.
  • the base material having the water-repellent layer of the invention is useful as an article (window glass or the like) for transport equipment (train, automobile, ship, aircraft, etc.).

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  • Laminated Bodies (AREA)

Abstract

Cette invention concerne un composé fluoré, une composition de revêtement, un matériau de base comportant une couche hydrophobe, et son procédé de production, la couche hydrophobe formée étant douée d'une hydrophobie (en particulier, une hydrophobie dynamique), d'une résistance à l'usure et d'une résistance aux intempéries suffisantes et ayant un impact relativement bas sur l'environnement. Cette invention utilise un composé fluoré représenté par RF-Y-Si(R1)3-n(X)n, où RF est un groupe perfluoroalkyle linéaire Cp, Y est un groupe fluoroalkylène linéaire Cq (qui peut inclure un atome d'oxygène de l'éther), l'extrémité terminale côté RF étant -CH2-, p est un nombre entier de 2 à 6, q est un nombre entier de 4 ou plus, p+q est un nombre entier de 10 ou plus, R1 est un groupe hydrocarbure monovalent, X est un groupe hydrolysable, et n est un nombre entier de 1 à 3.
PCT/JP2011/078612 2010-12-14 2011-12-09 Composé fluoré, composition de revêtement, matériau de base comportant une couche hydrophobe, et son procédé de production WO2012081524A1 (fr)

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JP2017537970A (ja) * 2014-12-19 2017-12-21 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ フッ素化合物
EP3202768A4 (fr) * 2014-09-30 2018-02-21 Unimatec Co., Ltd. Composé alkyl silane fluoré et son procédé de production
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WO2019039083A1 (fr) * 2017-08-22 2019-02-28 Ａｇｃ株式会社 Composé contenant du fluor, composition, solution de revêtement et procédé de production d'un composé contenant du fluor

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KR102134280B1 (ko) * 2018-03-30 2020-07-16 한국생산기술연구원 일액형 발수 코팅액 제조방법 및 이의 발수 코팅 필름 제조방법

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US10125154B2 (en) 2014-09-30 2018-11-13 Unimatec Co., Ltd. Fluorine-containing alkylsilane compound, and method for producing the same
CN106795073A (zh) * 2014-09-30 2017-05-31 优迈特株式会社 多氟烷基烯丙基化合物及其制备方法
KR102523918B1 (ko) 2014-09-30 2023-04-20 유니마테크 가부시키가이샤 폴리플루오로알킬알릴 화합물 및 그 제조법
EP3202768A4 (fr) * 2014-09-30 2018-02-21 Unimatec Co., Ltd. Composé alkyl silane fluoré et son procédé de production
EP3202756A4 (fr) * 2014-09-30 2018-06-06 Unimatec Co., Ltd. Composé polyfluoroalkylallyle, et procédé de fabrication de celui-ci
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JP2017537970A (ja) * 2014-12-19 2017-12-21 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ フッ素化合物
JPWO2018159641A1 (ja) * 2017-03-02 2019-12-19 Ａｇｃ株式会社 含フッ素シラン化合物の製造方法及び含フッ素シラン化合物
WO2018159641A1 (fr) * 2017-03-02 2018-09-07 Ａｇｃ株式会社 Procédé de production d'un composé de silane contenant du fluor, et composé de silane contenant du fluor
JP7405613B2 (ja) 2017-03-02 2023-12-26 Ａｇｃ株式会社 含フッ素シラン化合物の製造方法及び含フッ素シラン化合物
WO2019039083A1 (fr) * 2017-08-22 2019-02-28 Ａｇｃ株式会社 Composé contenant du fluor, composition, solution de revêtement et procédé de production d'un composé contenant du fluor
JPWO2019039083A1 (ja) * 2017-08-22 2020-10-15 Ａｇｃ株式会社 含フッ素化合物、組成物、コーティング液、および含フッ素化合物の製造方法

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