WO2019039083A1 - Composé contenant du fluor, composition, solution de revêtement et procédé de production d'un composé contenant du fluor - Google Patents

Composé contenant du fluor, composition, solution de revêtement et procédé de production d'un composé contenant du fluor Download PDF

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WO2019039083A1
WO2019039083A1 PCT/JP2018/024656 JP2018024656W WO2019039083A1 WO 2019039083 A1 WO2019039083 A1 WO 2019039083A1 JP 2018024656 W JP2018024656 W JP 2018024656W WO 2019039083 A1 WO2019039083 A1 WO 2019039083A1
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compound
group
fluorine
containing compound
carbon atoms
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PCT/JP2018/024656
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Japanese (ja)
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淳 渡壁
達也 宮嶋
俊文 柿内
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Ａｇｃ株式会社
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    • 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
    • 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

Definitions

  • the present invention relates to a fluorine-containing compound, a composition containing the fluorine-containing compound, a coating solution containing the fluorine-containing compound, and a method of producing the fluorine-containing compound.
  • the fluorine-containing compound has low friction, water and oil repellency, low refractive index, low dielectric constant, and the like, and therefore, is suitably used as a coating liquid for imparting the above-described properties to the surface of various substrates.
  • compounds having a perfluoropolyether group instead of a perfluoroalkyl group in the above-mentioned fluorine-containing silane compounds are known.
  • the compound having a perfluoropolyether group for example, CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CH 2 CH 2 -SiR 3-n X n (R is an alkyl as described in Patent Document 1) group, X represents a hydrolyzable group, n represents 1, 2, 3.) and, F described in Patent Document 2 [CF (CF 3) CF 2 O] a (CF 2) b CH 2 CH 2 -SiR (3-c) Cl c (R is an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 7, b is an integer of 2 to 8, c is an integer of 1 to 3), etc. It has been known.
  • the fluorine-containing compounds described in Patent Documents 1 and 2 and Non-Patent Document 1 are compounds having one hydrolyzable silyl group. In these techniques, the adhesion between the fluorine-containing compound and the substrate may be insufficient. Although it is conceivable to increase the number of hydrolyzable silyl groups in the molecule in order to improve the adhesion to the substrate, the synthesis was likely to be complicated.
  • An object of the present invention is to provide a novel fluorine-containing compound having two or more hydrolyzable silyl groups, which can be expected to improve adhesion to a substrate, and a simple production method thereof.
  • R 1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms
  • Y 1 is a hydrolyzable group or Z
  • R 4 is a single bond or an alkylene group having 1 to 6 carbon atoms
  • m is an integer of 1 to 3
  • Z is -R 5 SiR 2 3-n Y 2 n
  • R 2 is a monovalent hydrocarbon group having 1 to 6 carbon atoms
  • Y 2 is a hydrolyzable group
  • R 5 is an alkylene group having 1 to 6 carbon atoms
  • n is an integer of 1 to 3
  • Rf is a polyfluoroalkyl group optionally having an etheric oxygen atom having a formula weight of 50 to 10,000
  • Two or more R 1 , R 2 , R 4 , R 5 , Y 1 , Y 2 , m, n and Rf may be the same or different.
  • composition comprising the fluorine-containing compound of any one of the above [1] to [5] in a ratio such that the purity of the compound by gas chromatography is 60% or more with respect to the total amount of the composition.
  • composition comprising a compound represented by the following formula 9.
  • R 1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms
  • Y 11 is a hydrolyzable group
  • R 4 is a single bond or an alkylene group having 1 to 6 carbon atoms
  • m is an integer of 1 to 3
  • Rf is a polyfluoroalkyl group optionally having an etheric oxygen atom having a formula weight of 50 to 10,000;
  • R 1 , R 4 , Y 11 , m and Rf in a plurality of cases may be the same or different.
  • a coating liquid comprising the fluorinated compound of any one of the above [1] to [5] or the composition of [6] or [7], and a liquid medium.
  • the surface layer is treated by a dry coating method using the fluorine-containing compound of any one of the above [1] to [5] or the composition of [6] or [7] A method of manufacturing an article, which is formed on the surface of a material.
  • a method for producing an article wherein the coating liquid of [8] is applied to the surface of a substrate by a wet coating method, the liquid medium is removed, and a surface layer is formed on the surface of the substrate.
  • R 1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms
  • Y 11 is a hydrolyzable group
  • R 4 is a single bond or an alkylene group having 1 to 6 carbon atoms
  • m is an integer of 1 to 3
  • Rf is a polyfluoroalkyl group optionally having an etheric oxygen atom having a formula weight of 50 to 10,000;
  • R 1 , R 4 , Y 11 , m and Rf in a plurality of cases may be the same or different.
  • the production method of [13], wherein the coupling reaction is a coupling reaction using an organic peroxide and a hydrogen-containing organic compound.
  • R 1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms
  • Y 11 is a hydrolyzable group
  • R 4 is a single bond or an alkylene group having 1 to 6 carbon atoms
  • m is an integer of 1 to 3
  • Rf is a polyfluoroalkyl group optionally having an etheric oxygen atom having a formula weight of 50 to 10,000
  • Plural R 1 s and Y 11 s may be the same or different.
  • a novel fluorine-containing compound and a method for producing the same are provided.
  • the definitions of expressions and terms in the present invention are as follows.
  • the compound or group represented by the formula is represented as the compound or group numbered in the formula, and for example, the compound represented by formula 1 is described as "compound 1".
  • the "fluorine-containing compound” means a compound having a fluorine atom bonded to a carbon atom.
  • Iodine-containing compound means a compound having an iodine atom bonded to a carbon atom.
  • the “hydrogen-containing organic compound” means a compound having a hydrogen atom bonded to a carbon atom.
  • the "fluorine-containing group” means a group having a fluorine atom bonded to a carbon atom.
  • etheric oxygen atom is an oxygen atom that forms an ether bond between carbon and carbon atoms.
  • polyfluoro (poly) ether group is a generic term for a polyfluoroether group having one etheric oxygen atom and a polyfluoropolyether group having a plurality of etheric oxygen atoms in the polyfluoroalkyl group.
  • hydrolyzable silyl group is a group capable of forming a silanol group (Si—OH) by a hydrolysis reaction. For example, it is -SiR 13 -m Y 1 m of compound 1.
  • the "10-hour half-life temperature" of the radical initiator means a temperature at which the concentration of the radical initiator becomes half after 10 hours at a concentration of 0.1 mol / l in benzene, and the application temperature of the radical initiator is determined It is one of the indicators for
  • the "10-hour half-life temperature” of organic peroxide means the temperature at which the concentration of organic peroxide becomes half after 10 hours at a concentration of 0.1 mol / l in benzene, and the application of organic peroxide It is one of the indicators for determining the temperature.
  • “Purity by gas chromatography” means purity [%] determined from the peak area of a gas chromatogram obtained by analysis with a gas chromatograph equipped with a FID detector.
  • the fluorine-containing compound of the present invention is compound 1.
  • Compound 1 has one hydrogen atom directly bonded to each of two adjacent carbon atoms (C—C), one hydrolyzable silyl group bonded via R 4 , and one more The fluorine-containing group represented by Rf of is attached via a methylene group.
  • R 1 is a monovalent hydrocarbon group having 1 to 6 carbons
  • Y 1 is a hydrolyzable group or Z
  • R 4 is a single bond or an alkylene group having 1 to 6 carbons
  • Z is -R 5 SiR 2 3-n Y 2 n
  • R 2 is a monovalent hydrocarbon group having 1 to 6 carbon atoms
  • Y 2 is hydrolyzable.
  • R 5 is an alkylene group having 1 to 6 carbon atoms
  • n is an integer of 1 to 3
  • R f is a polyfluoro group which may have an etheric oxygen atom having a formula weight of 50 to 10,000.
  • R 1 , R 2 , R 4 , R 5 , Y 1 , Y 2 , m, n and Rf in the case of multiple alkyl groups may be the same or different.
  • Compound 1 preferably has a symmetrical structure. That R 1 to plural, R 4, Y 1, it is preferable m and Rf are the same, respectively.
  • the plurality of silyl groups are preferably the same from the viewpoint of easiness of production and uniformity of hydrolysis / condensation reaction.
  • the fluorine-containing group (Rf) possessed by the compound 1 is present on the surface (surface opposite to the substrate) of the surface layer without participating in the hydrolysis / condensation reaction involving the silanol group described later. Thereby, the surface of the surface layer has properties such as water repellency, oil repellency, stain resistance, low fingerprint adhesion, fingerprint removability, low friction, and the like.
  • the surface layer tends to have a low refractive index and a low dielectric constant, and can be used as an antireflective material or an insulating material in an electronic component, an electronic device or a wire coating.
  • the compound 1 since the hydrolyzable silyl group is respectively bonded to the adjacent two carbon atoms, the compound 1 is likely to be firmly adhered to the substrate. Further, since the compound 1 has two fluorine-containing groups, the fluorine-containing groups are densely oriented in the surface layer.
  • the hydrolyzable silyl group in the compound 1 is hydrolyzed to form a silanol group, and the silanol group is reacted between molecules to produce Si-O- A Si bond is formed, or the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (base -OH) on the surface of the base to form a chemical bond (base -O-Si). That is, the surface layer in the present invention contains Compound 1 in a state in which a part or all of the hydrolyzable silyl group of Compound 1 has been subjected to a hydrolysis reaction and a dehydration condensation reaction.
  • R 1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • the hydrocarbon group includes an alkyl group, a cycloalkyl group, an alkenyl group, an allyl group and a phenyl group. From the viewpoint of simplicity of synthesis, R 1 is preferably a monovalent alkyl group, and the carbon number thereof is preferably 1 to 3, and more preferably 1 to 2.
  • Y 1 is a hydrolyzable group or Z.
  • the hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. That, Si-Y 1 of the compound 1 is a silanol group (Si-OH) by hydrolysis.
  • the silanol groups further react intermolecularly to form Si-O-Si bonds.
  • the silanol group undergoes a dehydration condensation reaction with a hydroxyl group on the surface of the base (base -OH) to form a chemical bond (base -O-Si).
  • hydrolyzable group Y 1 examples include an alkoxy group, a halogen atom, an acyl group and an isocyanate group (—NCO).
  • the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.
  • a halogen atom a chlorine atom, a bromine atom and an iodine atom are preferable, and a chlorine atom is particularly preferable.
  • an alkoxy group or a halogen atom is preferable from the viewpoint of easy preparation of the compound 1.
  • an alkoxy group having 1 to 4 carbon atoms is preferable from the viewpoint that the amount of outgassing at the time of coating is small and the storage stability of the compound 1 is excellent. Long-term storage stability of the compound 1 is necessary In such a case, an ethoxy group is particularly preferable, and a methoxy group is particularly preferable when the reaction time after coating is to be short.
  • R 2 is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Preferred forms of R 2 are the same as preferred forms of R 1 .
  • Y 2 is a hydrolyzable group. The preferred form of Y 2 is the same as the preferred form when Y 1 is a hydrolyzable group.
  • R 5 is an alkylene group having 1 to 6 carbon atoms. As R 2 , a linear alkylene group is preferable from the viewpoint of easy synthesis, and the carbon number thereof is preferably 2 to 4 and particularly preferably 3.
  • m is an integer of 1 to 3. m is preferably 2 or 3, and more preferably 3.
  • the presence of a plurality of Y 1 in the group (—SiR 13 -m Y 1 m ) tends to make the bond with the surface of the substrate stronger.
  • m is 2 or more, a plurality of Y 1 present in one molecule may be the same as or different from each other. It is preferable that the raw materials are the same as each other because they are easily available and easily manufactured.
  • n is an integer of 1 to 3. n is preferably 2 or 3, and more preferably 3. Due to the presence of a plurality of Y 2 in the hydrolyzable silyl group (—SiR 2 3 ⁇ n Y 2 n ), the bond with the surface of the substrate tends to be stronger. When n is 2 or more, a plurality of Y 2 present in one molecule may be the same as or different from each other. It is preferable that the raw materials are the same as each other because they are easily available and easily manufactured.
  • the group (-SiR 13 -m Y 1 m ) is a hydrolyzable silyl group (when Y 1 is a hydrolyzable group), the group is —Si (OCH 3 ) 3 or —SiCH 3 (OCH 3 ) 2 , -Si (OCH 2 CH 3 ) 3 , -SiCl 3 , -Si (OC (O) CH 3 ) 3 and -Si (NCO) 3 are preferable.
  • -Si (OCH 3 ) 3 is particularly preferred from the viewpoint of ease of handling in industrial production.
  • R 4 is a single bond or an alkylene group having 1 to 6 carbon atoms.
  • R 4 a single bond or a linear alkylene group is preferable, and a single bond is particularly preferable, from the viewpoint of the coupling reaction described later.
  • Rf is a polyfluoroalkyl group which may have an etheric oxygen atom having a formula weight of 50 to 10,000. That is, R f is a polyfluoroalkyl group or a polyfluoro (poly) ether group having a predetermined formula weight. Two R f in compound 1 may be the same or different. It is preferable that they are the same from the viewpoint of the ease of manufacture and the uniformity of the surface layer described later.
  • the formula weight of Rf is preferably 51 to 6000, and more preferably 69 to 1000.
  • Rf (the site for bonding to a methylene group, ie, the bonding site on the silyl group side) is a difluoromethylene group (—F 2 C—) or a trifluoromethyl fluoromethylene group (— (CF 3 ) FC— Is preferred.
  • Rf is preferably a perfluoroalkyl group which may have an etheric oxygen atom in view of chemical durability. When R f is a perfluoroalkyl group (having no etheric oxygen atom), it is preferably a C 1-20 perfluoroalkyl group represented by the following R F1 .
  • R f is preferably a group 2 (polyfluoro (poly) ether group) in view of chemical durability and easiness of production.
  • R F1 is a perfluoroalkyl group having 1 to 20 carbon atoms
  • R f1 is a fluoroalkylene group
  • j is an integer of 2 to 500
  • a plurality of (OR f1) is the number of carbon atoms It may consist of two or more different types (OR f1 ).
  • R F1 is a C 1-20 perfluoroalkyl group.
  • the perfluoroalkyl group is preferably linear.
  • a perfluoroalkyl group having 1 to 10 carbon atoms is preferable, a perfluoroalkyl group having 1 to 6 carbon atoms is more preferable, and a perfluoroalkyl group having 1 to 3 carbon atoms is more preferable in terms of further excellent lubricity and friction resistance in the surface layer. Is particularly preferred.
  • RF 1 examples include CF 3- , CF 3 CF 2- , CF 3 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2 CF 2 -, CF 3 CF (CF 3) - , and the like.
  • CF 3 ⁇ , CF 3 CF 2 ⁇ , and CF 3 CF 2 CF 2 ⁇ are preferable from the viewpoint that the initial water / oil repellency, abrasion resistance, and fingerprint stain removability of the surface layer are further excellent.
  • R f1 is a fluoroalkylene group.
  • the carbon number of R f1 is preferably 1 to 6 from the viewpoint that the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent.
  • R f1 a perfluoroalkylene group is preferable, and a linear perfluoroalkylene group is more preferable, from the viewpoint that the friction resistance and the lubricity of the surface layer are further excellent.
  • the proportion of the perfluoroalkylene group in the total R f1 is preferably 60 mol% or more, more preferably 80 mol% or more, and particularly preferably 100 mol% from the viewpoint that the friction resistance and the lubricity of the surface layer are further excellent.
  • J is preferably an integer of 2 to 200, more preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 100. If j is at least the lower limit value of the above range, the water and oil repellency of the surface layer is further excellent. If j is below the upper limit of the said range, the abrasion resistance of a surface layer will be further excellent. That is, when the number average molecular weight of the compound 1 is too large, the number of hydrolyzable silyl groups present per unit molecular weight decreases, and the abrasion resistance of the surface layer decreases.
  • each OR f1 when two or more types of OR f1 exist, the binding order of each OR f1 is not limited. For example, if OCF 2 and OCF 2 CF 2 are present, OCF 2 and OCF 2 CF 2 may be randomly, alternately arranged in blocks.
  • the two or more OR f1 is present, that there are two or more OR f1 of different carbon number, the number of hydrogen atoms are present two or more different OR f1, two position of the hydrogen atoms are different.
  • the structure represented by ⁇ (OCF 2 ) j 1 (OCF 2 CF 2 ) j 2 ⁇ includes j 1 (OCF 2 ) and j 2 (OCF 2 CF 2) And are randomly arranged.
  • the structure represented by (OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2) j3 is a j3 amino (OCF 2 CF 2) and j3 amino (OCF 2 CF 2 CF 2 CF 2) Indicates that they are alternately arranged.
  • (OR f1 ) j one having the following structure in at least a part of (OR f1 ) j is preferable.
  • j1 is an integer of 1 or more
  • j2 is an integer of 1 or more
  • j1 + j2 is an integer of 2 to 500
  • j3 and j4 are integers of 2 to 500
  • j5 is 1 to J6 and j7 are integers of 1 or more
  • j6 + j7 is an integer of 2 to 500
  • j8 is an integer of 1 to 250.
  • R f may be a polyfluoroalkyl group having a hydrogen atom bonded to a carbon atom.
  • groups 6 and 7 can be exemplified.
  • R F2 is a linear perfluoroalkyl group having carbon number p1, p1 is an integer of 2 to 6, r1 is an integer of 1 or more, and p1 + r1 is an integer of 6 or more.
  • R F3 is a linear perfluoroalkyl group having a carbon number p2
  • p2 is an integer of 2 ⁇ 6, - (CH 2 CF 2) s - (CF 2 CF 2) t - is, s
  • It is a structure in which-(CH 2 CF 2 ) -units and t-(CF 2 CF 2 ) -units are connected in the order described, s is an integer of 1 to 20, and t is P is an integer of 1 to 10, and p2 + 2s + 2t is an integer of 8 or more.
  • -SiR 13 -m Y 1 m is -Si (OR 3 ) 3
  • R 4 is a single bond
  • R f is group 2
  • the formula weight is 50
  • R 3 is a linear alkyl group having 1 to 4 carbon atoms or an alkyl group having a branch having 3 or 4 carbon atoms
  • a linear alkyl group having 1 to 2 carbon atoms is preferable.
  • the production method of the present invention is a production method of the fluorine-containing compound 11 in which the iodine-containing compound 3 is subjected to a coupling reaction.
  • the method of producing compound 11 is the method of producing compound 1.
  • compound 1 can be obtained by further reacting compound 11 as described later.
  • R 1 , R 4 , m and Rf are as described above, and Y 11 is a hydrolyzable group.
  • R 1 , R 4 , Y 11 , m and Rf in a plurality of cases may be the same or different.
  • the coupling reaction is a deiodine coupling reaction.
  • the method of this coupling reaction is not particularly limited. For example, a method using an organic peroxide and a hydrogen-containing organic compound, a method using a copper compound, and the like can be mentioned.
  • a coupling reaction using an organic peroxide and a hydrogen-containing organic compound (hereinafter, also referred to as “coupling reaction A”) is preferable in that it can react inexpensively without using transition metals.
  • a compound having a group 8 hereinafter, referred to as “compound 81”) is preferable.
  • -CHR 11 -CHR 12 -CHR 13 - 8 However, R 11 , R 12 and R 13 each independently represent a hydrogen atom or an alkyl group.
  • Coupling reaction A is assumed to proceed as follows. First, the organic peroxide abstracts a hydrogen atom from the hydrogen-containing organic compound to generate a radical. Next, a radical derived from the hydrogen-containing organic compound extracts an iodine atom from the compound 3 to generate a radical derived from the compound 3. Then, two radical molecules derived from the compound 3 are combined to form a compound 11. When one type of compound is used as the compound 3, symmetrical compounds 11 (a compound in which two Rf, R 4 and -SiR 13 -m Y 11 m are respectively the same) are obtained. When two or more kinds of compounds are used as the compound 3, an asymmetric compound 11 is obtained.
  • a hydrogen radical is added to the radical derived from the compound 3, so that a side reaction in which the compound 9 is by-produced is present, so it is preferable to suppress the side reaction.
  • R 1 , R 4 , m, Rf and Y 11 are as described above.
  • intermediates, by-products and target substances to be obtained are generally measured by 1 H-NMR, 13 C-NMR, 19 F-NMR, FT-IR, GC-MS, elemental analysis, etc. Can be identified and confirmed by 1 H-NMR, 13 C-NMR, 19 F-NMR, FT-IR, GC-MS, elemental analysis, etc. Can be identified and confirmed by 1 H-NMR, 13 C-NMR, 19 F-NMR, FT-IR, GC-MS, elemental analysis, etc. Can be identified and confirmed by 1 H-NMR, 13 C-NMR, 19 F-NMR, FT-IR, GC-MS, elemental analysis, etc. Can be identified and confirmed by
  • iodine-containing compound 3 can be produced by reacting iodine-containing compound 4 with silicon-containing compound 5 in the presence of a radical initiator.
  • Rf-I 4 CH 2 CH-R 4 -SiR 1 3-m Y 11 m 5
  • R 1 , R 4 , Y 11 , Rf and m are as described above.
  • the ratio of the compound 4 to the compound 5 to be reacted is preferably a ratio of 0.8 to 10 moles of the compound 5 to 1 mole of the compound 4, and more preferably a ratio of 1 to 5 moles. By setting it as the said ratio, since the reaction rate of the compound 4 is raised and it is easy to suppress the quantity of the unreacted compound 5, it is preferable.
  • a peroxide and an azo compound are mentioned, for example.
  • the peroxide include peroxyketal, diacyl peroxide, peroxydicarbonate, peroxy ester, hydroperoxide, dialkyl peroxide, ketone peroxide, inorganic peroxide, and fluorine-containing peroxide.
  • the azo compound include azonitrile, azoamide, azoamidine and azoimidazoline.
  • the 10-hour half-life temperature of the radical initiator is preferably 0 to 150 ° C., more preferably 20 to 100 ° C., and still more preferably 30 to 80 ° C. If the said half life temperature is in the said range, it will be easy to control reaction rate.
  • the amount of the radical initiator added is preferably 0.001 to 2 mol%, more preferably 0.01 to 1 mol%, based on 100 mol% of the compound 4.
  • a solvent As a solvent, an organic solvent is preferable and a fluorine-containing organic solvent is more preferable.
  • the fluorine-containing organic solvent the same solvents as the solvents used in the coupling reaction A described below can be used.
  • the amount of solvent is preferably 0 to 99.9% by mass with respect to the total amount of the reaction solution.
  • the reaction for producing the iodine-containing compound 3 it is preferable to perform heating in order to allow efficient reaction taking into consideration the decomposition temperature of the radical initiator.
  • the heating temperature when the 10-hour half-life temperature of the radical initiator and T 1 °C, (T 1 -10 ) ⁇ (T 1 +50) °C preferably, T 1 ⁇ (T 1 +30 ) °C more preferably From the viewpoint of operation, 40 to 120 ° C. is preferable. Within the above temperature range, the yield of compound 3 tends to be high.
  • the heating time is preferably 1 to 24 hours. In order to avoid rapid radical initiator decomposition, the reaction time is preferably 1 hour or more, and preferably 24 hours or less from the viewpoint of productivity.
  • the compound 3 can be purified from the reaction solution obtained by reacting the compound 4 and the compound 5 by a conventional method, and can be subjected to a coupling reaction.
  • the reaction rate of the compound 4 and the compound 5 is high, the compound may be subjected to a coupling reaction without purification.
  • the reaction rate of the compound 4 and the compound 5 is preferably 80% or more, and more preferably 90% or more.
  • the Y 11 of the resulting compound 3, convert to different types of Y 11, it may be subjected to coupling reaction.
  • Y 11 is, Cl
  • OR Y 11 is, Cl
  • the coupling reaction may be carried out after obtaining Compound 3 converted to 3 (R 3 is as described above). Thereby, the compound 11 whose Y 11 is OR 3 is obtained.
  • Y 11 of compound 11 may be converted to Y 11 of a type different from Y 11 of compound 3.
  • Y 11 is, Cl, with a compound 4 is Br or I
  • Y 11 is Cl, to give the compound 3 is Br or I
  • then subjected to coupling reaction Y 11 is Cl, Br or I to obtain the compound 11 is, by converting the Y 11 compounds 11 to OR 3, to give a compound 11 Y 11 is OR 3.
  • the compound 11 whose Y 11 is OR 3 is obtained.
  • Organic peroxide As an organic peroxide used for the coupling reaction A, for example, dialkyl peroxide, peroxyketal, diacyl peroxide, dialkyl peroxydicarbonate, peroxy ester, peroxy monocarbonate, bis (fluoroacyl) peroxide, bis (chlorofluoroacyl) And peroxides and peroxy esters.
  • organic peroxides include di-tert-butyl peroxide, perfluorodi-tert-butyl peroxide, dialkyl peroxides such as tert-butylcumyl peroxide, dicumyl peroxide, etc.
  • Diacyl peroxides di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, dialkylperoxydicarbonates such as di-methoxybutylperoxydicarbonate Carbonate, cumylperoxyneodecanate, 1,1,3,3-tetramethylbutylperoxyneodecanate, tert-hexylperoxyneodecanate, tert-amyl peroxyneodecanate, ter -Butyl peroxy neodecanate, tert-butyl peroxy neooctanate, tert-butyl peroxy neohexanate, tert-butyl peroxypiperate, tert-butyl-2-ethyl hexanate, tert-buty
  • the 10-hour half-life temperature of the organic peroxide is preferably 10 to 150 ° C., more preferably 15 to 120 ° C., and still more preferably 20 to 80 ° C. If the said half life temperature is in the said range, it will be easy to control reaction rate. As the organic peroxide is easy to control the reaction temperature, diisopropyl peroxydicarbonate and tert-butyl peroxypiperate are preferred.
  • the total number of moles of the organic peroxide used for the coupling reaction A is preferably 0.0005 to 5 times the total number of moles of the iodine atom of the compound 3. It is easy to adjust the conversion rate of reaction as it is in the said range. It is more preferably 0.005 to 3 times, still more preferably 0.05 to 2 times, and particularly preferably 0.1 to 1 times. Further, the concentration of the organic peroxide in the reaction solution is preferably 5% by mass or less, more preferably 1% by mass or less, because it is easy to adjust to an appropriate reaction rate. The side reaction can be more easily suppressed as the amount of the organic peroxide added is larger.
  • the hydrogen-containing organic compound 81 is a hydrogen-containing organic compound having a group 8.
  • R 11 , R 12 and R 13 is independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.
  • the hydrogen-containing organic compound 81 is not particularly limited as long as it is a compound having a group 8, and may be a compound having an etheric oxygen atom or another functional group.
  • a linear or branched chain saturated hydrocarbon (alkane) or a saturated alicyclic hydrocarbon which may have a substituent is easy to handle and has high reaction activity, It is preferable in that it is less likely to cause a reaction.
  • the carbon number of the hydrogen-containing organic compound 81 is preferably 3 to 16, and more preferably 4 to 12, from the viewpoint of good reactivity.
  • alkane examples include n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methyl Hexane, 2,4-dimethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 2 -Methyl-3-ethylpentane, 3-methyl-3-ethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, 2,2,3-trimethylpentane, 2-methylheptane, 2 , 2,4-trimethylpentane, n-nonane, 2,2,5-trimethylhexane, n
  • the total number of moles of the hydrogen-containing organic compound 81 used in the coupling reaction A is preferably 2 to 500 times the total number of moles of all iodine atoms in the compound 3.
  • the amount of the hydrogen-containing organic compound 81 is two or more, the iodine in the compound 3 is easily extracted, and the reaction yield of the compound 11 is easily improved.
  • the amount of the hydrogen-containing organic compound 81 is 500 times or less, the fluorine-containing compound 3 is easily dissolved, and the concentration of the compound 3 is hardly reduced. 5 to 300 times is more preferable, and 10 to 100 times is more preferable.
  • solvent solvent
  • an organic solvent is mentioned, A fluorine-containing organic solvent is preferable.
  • fluorine-containing organic solvent examples include perfluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons and hydrofluoroethers.
  • perfluorocarbons examples include n-perfluorohexane, n-perfluoroheptane, perfluorocyclobutane, perfluorocyclohexane and perfluorobenzene.
  • hydrochlorofluorocarbons for example, 2,2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, 1,1-dichloro-2,2,3,3,3 And-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane.
  • hydrofluorocarbon for example, 1,1,2,2-tetrafluorocyclobutane, CF 3 CF 2 CH 2 CH 3 , CF 3 CHF (CF 2 ) 3 F, CF 3 (CF 2 ) 4 H, CF 3 CF 2 CHF (CF 2 ) 2 F, CF 3 (CHF) 2 (CF 2 ) 2 F, CHF 2 CHF (CF 2 ) 3 F, CF 3 (CF 2 ) 5 H, CF 3 CH (CF 3 ) (CF 2) 3 F, CF 3 CF (CF 3) CHF (CF 2) 2 F, CF 3 CF (CF 3) (CHF) 2 CF 3, CF 3 CH (CF 3) CHF (CF 2) 2 F, CF 3 (CF 2) 3 (CH 2) 2 H and the like.
  • the hydrofluorocarbon for example, 1,1,2,2-tetrafluorocyclobutane, CF 3 CF 2 CH 2 CH 3 , CF 3 CHF (CF 2 ) 3 F, CF 3 (CF
  • hydrofluoroethers examples include CF 3 CH 2 O (CF 2 ) 2 H, CHF 2 CF 2 CH 2 O (CF 2 ) 2 H, CH 3 O (CF 2 ) 4 H, and CH 3 OCF 2 CF CF 3) 2, CF 3 CHFCF 2 OCF 3 , and the like.
  • a solvent compatible with both the fluorine-containing compound 3 as a reaction substrate and the hydrogen-containing organic compound 81 to be added is preferable.
  • a hydrochlorofluorocarbon is preferable.
  • Dichloro-1,1,2,2,3-pentafluoropropane is mentioned.
  • the concentration of the compound 3 in the case of using a solvent is preferably 0.1 to 50% by mass with respect to the total amount of the reaction solution. 0.1 mass% or more is preferable from a viewpoint of productivity, and 50 mass% or less is preferable from a viewpoint which prevents rapid heat_generation
  • the concentration of the compound 3 is preferably 0.5% by mass or more, and more preferably 3% by mass or more because the formation of the compound 8 is easily suppressed.
  • the concentration of the hydrogen-containing organic compound 81 in the case of using a solvent is preferably 0.1 to 50% by mass with respect to the total amount of the reaction solution. It is easy to become a moderate reaction rate as it is 0.1 mass% or more.
  • the hydrogen-containing organic compound 81 can also be used as a solvent. From the viewpoint of securing the compatibility with the compound 3, the concentration of the hydrogen-containing organic compound 81 is preferably 50% by mass or less, and more preferably 1 to 30% by mass.
  • the coupling reaction A is preferably heated for efficient processing taking into consideration the decomposition temperature of the organic peroxide.
  • the heating temperature at this time is preferably T 2 to (T 2 +80) ° C., and (T 2 +10) to (T 2 +50) ° C., where the 10 hour half-life temperature of the organic peroxide is T 2 ° C. Is more preferable, and from the viewpoint of operation, 50 to 150 ° C. is preferable.
  • the higher the heating temperature the easier it is to suppress the formation of by-products. It is presumed that the decomposition of the organic peroxide occurs rapidly, the radical derived from the compound 3 is easily generated, and the reaction between the radicals derived from the compound 3 easily occurs.
  • the heating temperature is preferably 50 ° C.
  • the heating time is preferably 1 to 24 hours. In order to avoid rapid decomposition of the organic peroxide, one hour or more is preferable. Moreover, it is preferable that it is less than 24 hours from a viewpoint of productivity.
  • Coupling reaction A using an organic peroxide and a hydrogen-containing organic compound does not require a metal catalyst. Therefore, the compound 11 obtained by this method can be inexpensively manufactured without using a metal catalyst such as platinum which is usually used for hydrosilylation reaction.
  • compound 11 may be obtained by purifying the reaction solution containing compound 11 obtained by a conventional method.
  • Y 1 is Z in compound 1
  • Y 11 is further reacted to obtain compound 1 in which Y 1 is Z.
  • Z is -SiCH 3 (CH 2 CH 2 CH 2 -SiCH 3 (OCH 3 ) 2 ) 2 (compound 1-A1) and -Si (CH 2 CH 2 CH 2 -Si (OCH 3 ) 3 ) 3 (compound 1-B1) can be synthesized by the following route.
  • Compound 1-A is obtained as Compound 1. This is reacted with a Grignard reagent followed by hydrosilylation to give compound 1-A1.
  • the compound 1-A may be an alkyldihalogenosilyl group (specifically, a methyl dichlorosilyl group) in place of the alkyldialkoxysilyl group (specifically, a methyldimethoxysilyl group).
  • the compound 1-B may be a trihalogenosilyl group (specifically, trichlorosilyl group) instead of the trialkoxysilyl group (specifically, trimethoxysilyl group).
  • Examples of Grignard reagents include allylmagnesium chloride and allylmagnesium bromide.
  • a platinum compound catalyst such as chloroplatinic acid may be used to react trialkoxysilane (in the above example, trimethoxysilane). These reactions are described, for example, in International Publication WO 2014/069592, Japanese Patent No. 6296200, and the like.
  • the composition of the present invention comprises Compound 1.
  • the composition of the present invention does not contain a liquid medium.
  • the composition may contain fluorine-containing compounds other than compound 1.
  • the other fluorine-containing compounds are fluorine-containing compounds (hereinafter referred to as “by-product fluorine-containing compounds”) by-produced in the production process of compound 1, known fluorine-containing compounds used in the same applications as compound 1, and Compounds unavoidable in production such as raw materials for the reaction may be mentioned.
  • As the other fluorine-containing compound a compound which is less likely to deteriorate the characteristics of Compound 1 is preferable.
  • As a by-product fluorine-containing compound the said compound 9 is mentioned.
  • the composition may also contain known additives other than the above-mentioned fluorine-containing compounds, such as an acid catalyst and a basic catalyst which promote the hydrolysis and condensation reaction of the hydrolyzable silyl group.
  • acid catalysts include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like.
  • the basic catalyst include sodium hydroxide, potassium hydroxide, ammonia and the like.
  • the content of the additive is preferably 0 to 10% by mass, particularly preferably 0 to 1% by mass, of the composition.
  • Purification is performed by known purification methods such as column purification and distillation under high vacuum conditions to increase the content of compound 1 in the composition.
  • the content of the compound 1 in the composition is preferably 60% or more, more preferably 70% or more, as the purity of the compound 1 by gas chromatography with respect to the total amount of the composition. If the content of Compound 1 in the composition is in the above range, the properties of Compound 1 such as water and oil repellency and low refractive index are likely to be sufficiently exhibited when the composition is used for coating a substrate .
  • the coating liquid of the present invention comprises Compound 1 or the composition of the present invention and a liquid medium.
  • the liquid medium means a solvent or a dispersion medium.
  • the coating solution may be a solution or a dispersion. A solution is preferred as it provides a uniform surface layer.
  • an organic solvent is preferable.
  • the organic solvent may be a fluorine-containing organic solvent, may be a non-fluorinated organic solvent, and may include both solvents.
  • fluorine-containing organic solvent examples include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and the like.
  • the fluorinated alkane is preferably a compound having 4 to 8 carbon atoms.
  • C 6 F 13 H Asahi Glass Co., Ltd., Asahi Klin (registered trademark) AC-2000
  • C 6 F 13 C 2 H 5 Asahi Glass Co., Ltd., Asahi Klin (registered trademark) AC-6000
  • C 2 F 5 CHFCHFCF 3 Kemers Corporation, Bartrel (registered trademark) XF
  • fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis (trifluoromethyl) benzene and the like.
  • the fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms.
  • Commercially available products include, for example, CF 3 CH 2 OCF 2 CF 2 H (Asahi Glass Co., Ltd., Asahiklin (registered trademark) AE-3000), C 4 F 9 OCH 3 (3M, Novec (registered trademark) 7100), C 4 F 9 OC 2 H 5 (manufactured by 3M, Novec (registered trademark) 7200), C 2 F 5 CF (OCH 3 ) C 3 F 7 (manufactured by 3M, Novec (registered trademark) 7300), etc. may be mentioned. .
  • fluorinated alkylamines include perfluorotripropylamine, perfluorotributylamine and the like.
  • fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol and hexafluoroisopropanol.
  • the fluorine-containing organic solvent used in the above-mentioned coupling reaction A may be used as the fluorine-containing organic solvent.
  • non-fluorinated organic solvent a compound consisting only of hydrogen atom and carbon atom and a compound consisting only of hydrogen atom, carbon atom and oxygen atom are preferable, and hydrocarbon organic solvents, alcohols, ketones, ethers and esters can be mentioned.
  • Preferred hydrocarbon organic solvents are hexane, heptane, cyclohexane, toluene and xylene.
  • As the alcohol methanol, ethanol, propanol and 2-propanol are preferable.
  • As the ketone acetone, methyl ethyl ketone and methyl isobutyl ketone are preferable.
  • As the ether tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methyl-t-butyl ether are preferable.
  • ester ethyl acetate and butyl acetate are preferable.
  • the non-fluorinated organic solvent is preferably a ketone from the viewpoint of the solubility of the compound 1.
  • the content of the compound 1 or the composition of the present invention is preferably 0.001 to 10% by mass, particularly preferably 0.01 to 1% by mass, of the present coating liquid.
  • the content of the liquid medium is preferably 90 to 99.999% by mass, particularly preferably 99 to 99.99% by mass, of the present coating liquid.
  • the article of the present invention (hereinafter also referred to as “the present article") has a surface layer formed of Compound 1 or the composition of the present invention on the surface of a substrate.
  • the surface layer contains Compound 1 in a state in which part or all of the hydrolyzable silyl group of Compound 1 has undergone a hydrolysis reaction and a dehydration condensation reaction.
  • the thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. If the thickness of the surface layer is equal to or more than the lower limit value of the above range, the effect by the surface treatment is easily obtained sufficiently. If the thickness of the surface layer is equal to or less than the upper limit value of the above range, the utilization efficiency is high.
  • the thickness of the surface layer is obtained by obtaining an interference pattern of the reflected X-ray by the X-ray reflectance method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU, ATX-G) It can be calculated.
  • the substrate is not particularly limited as long as the substrate is required to be imparted with water and oil repellency.
  • Materials of the substrate include glass, plastic, ceramic, quartz, sapphire, metal, metal oxide, paper, cloth, stone, and composite materials of these.
  • the glass may be chemically strengthened.
  • a base film such as a SiO 2 film may be formed on the surface of the base material.
  • a substrate for a touch panel and a substrate for a display are suitable, and a substrate for a touch panel is particularly suitable. That is, as an article, an article having a surface layer on the surface of a member that constitutes a surface touched by a finger of a touch panel is preferable.
  • As a material of the base material for touchscreens glass or transparent resin is preferable.
  • the article can be produced, for example, by the following method.
  • Examples of the dry coating method include methods such as vacuum deposition, CVD, and sputtering. From the viewpoint of suppressing the decomposition of the compound 1 and the convenience of the apparatus, the vacuum evaporation method is preferred. At the time of vacuum deposition, a pellet-like substance obtained by impregnating a porous metal body such as iron or steel with the compound 1 or the composition of the present invention may be used.
  • a spin coat method As a wet coating method, a spin coat method, a wipe coat method, a spray coat method, a squeegee coat method, a dip coat method, a die coat method, a bar coat method, an ink jet method, a flow coat method, a roll coat method, a cast method, Langmuir-bro The jet method, the gravure coating method, etc. may be mentioned.
  • reaction rates of nC 4 F 9 -I and vinyltrimethoxysilane were determined by analysis using GC that the ratio of the area of each compound after reaction to the area of AK225G was the area of each compound before reaction. Calculated as a ratio to the ratio to the area of AK225G.
  • the conversion of nC 4 F 9 -I was 96.3%, and the conversion of vinyltrimethoxysilane was 98.7%.
  • the peak of the compound 3-1 appeared as follows.
  • the autoclave After subjecting the mixture before reaction to GC analysis, the autoclave was immediately closed. Freeze degassing was repeated twice using liquid nitrogen. The internal temperature of the autoclave was about 0 ° C., and nitrogen gas was introduced so that the internal pressure was 0.3 MPaG. Thereafter, the autoclave was heated in a water bath and stirred at an internal temperature of 70 ° C. for 7 hours. The autoclave was removed from the water bath and allowed to stand overnight to obtain a reaction solution A containing compound 1-1. The reaction liquid A was subjected to GC analysis to find that the peak of the compound 3-1 disappeared, and it was confirmed that the product A identified as the compound 1-1 and the compound 9-1 were contained by the method described later. The ratio of the product A (compound 1-1) to the compound 9-1 in the reaction liquid A was 64.6: 35.4. n-C 4 F 9 -CH 2 -CH 2 -Si (OCH 3) 3 9-1
  • the obtained reaction liquid A and a stirrer were placed in an eggplant flask, and low boiling components such as a solvent were distilled off at 40 ° C. for 1 hour under reduced pressure.
  • the component (composition A) left in the eggplant flask was 2.41 g.
  • the GC purity of the product A (compound 1-1) in the composition A is 75%, and the yield of the product A (compound 1-1) determined on the assumption that GC area% is mass% is 60%. there were.
  • the product A was separated from the composition A and the structure was identified.
  • NMR measurement was analyzed by combining 1 H-NMR, 13 C-NMR, 1 H- 13 C HMQC method, 1 H- 13 C HMBC method, and 13 C DEPT method.
  • Example 2 The reaction was conducted in the same manner as in Example 1 except that the IPP addition amount in Example 1 was changed to 30% (0.536 g) described above, and AK225G to be added was changed to 38.52 g. %Met. The reaction gave compound 1-1 and fluorine-containing compound 9-1.
  • reaction liquid b containing compound 3-2.
  • the reaction rate was calculated in the same manner as Example 1.
  • the conversion of (HFPO) 3 -I was 98.2%, and the conversion of vinyltrimethoxysilane was 97.9%.
  • the 1 H-NMR of reaction liquid b was measured, and the peak of compound 3-2 appeared as follows. 1 H-NMR: 2.50 to 2.78 ppm (m): 1H, 2.80 to 3.13 (m): 2H, 3.62 ppn (s): 9H.
  • the obtained reaction liquid B and a stirrer are placed in an eggplant flask and heated at 47 ° C. for 2 hours under reduced pressure, then at 70 ° C. for 6 hours, then at 100 ° C. for 6 hours to distill low boiling point components such as solvents
  • the mixture was removed to obtain composition B containing compound 1-2.
  • the composition B obtained in the eggplant flask was 2.51 g.
  • the GC purity of the product B (compound 1-2) in the composition B is 87%, and the yield of the product B (compound 1-2) determined on the assumption that GC area% is mass% is 70%. there were.
  • reaction liquid c containing compound 3-3.
  • the reaction rate of each component was calculated in the same manner as in Example 1.
  • the conversion of PHVE-I was 97.8%, and the conversion of vinyltrimethoxysilane was 97.3%.
  • the 1 H-NMR of reaction liquid c was measured, and the peak of compound 3-3 appeared as follows.
  • the autoclave was immediately closed. Freeze degassing was repeated twice using liquid nitrogen.
  • the internal temperature of the autoclave was about 0 ° C., and nitrogen gas was introduced so that the internal pressure was 0.3 MPaG.
  • the autoclave was heated in a water bath and stirred at an internal temperature of 70 ° C. for 7 hours. The autoclave was removed from the water bath to obtain a reaction solution C containing compound 1-3.
  • Example 5 The compound 3-3 was synthesized by the following method in the same manner as in Example 4 except that the following conditions were adopted, and a compound 1-3 was produced using the obtained compound 3-3.
  • the autoclave was heated in a water bath and stirred at an internal temperature of 50 ° C. for 2 hours, at 60 ° C. for 2 hours, and at 70 ° C. for 2 hours.
  • the autoclave was removed from the water bath and allowed to cool to room temperature to obtain a reaction solution d containing compound 3-3.
  • the reaction solution d was analyzed by GC, and the reaction rate was calculated in the same manner as in Example 1.
  • the conversion of PHVE-I was 93.3%, and the conversion of vinyltrimethoxysilane was 99.6%.
  • the peak of compound 3-3 appeared at the same retention time as in Example 4.
  • the autoclave was heated in a water bath and stirred at an internal temperature of 70 ° C. for 7 hours.
  • the autoclave was removed from the water bath to obtain a reaction solution D containing compound 1-3 at normal temperature.
  • the reaction solution D was analyzed by GC, and the reaction rate was calculated in the same manner as Example 1.
  • the conversion of compound 3-3 was 89.9%, and the ratio of GC areas of compound 1-3 to compound 9-3 was 65.6: 34.4.
  • Example 6 The reaction solution d obtained in Example 5 was used. A reaction was performed in the same manner as in Example 5 except that the molar ratio of compound 3-3 / IPP / n-hexane was changed to 1 / 0.2 / 20 under the same assumption as in Example 5. The reaction rate of compound 3-3 was 10.4%. Compound 1-3 The GC area ratio of compound 9-3 was 53.2: 46.8.
  • Example 7 The reaction was carried out in the same manner as in Example 5 except that n-hexane was changed to isohexane. The conversion of compound 3-3 was 83.3%, and GC of compound 1-3 and compound 9-3 was obtained. The area ratio was 66.0: 34.0.
  • Example 8 The reaction was carried out in the same manner as in Example 5 except that the reaction temperature and time were changed to 50 ° C. for 2 hours, then to 60 ° C. for 2 hours and then to 70 ° C. for 2 hours.
  • the reaction rate was 96.4%, and the ratio of the GC area of compound 1-3 to compound 9-3 was 56.8: 43.2.
  • a fluorine-containing compound having two or more hydrolyzable silyl groups per molecule can be conveniently synthesized.
  • the fluorine-containing compound of the present invention can be used in various applications where it is required to impart lubricity and water and oil repellency.
  • a display input device such as a touch panel, a surface protection coat of a transparent glass or transparent plastic member, a spectacle lens, a camera lens, a medical device such as a stomach camera, a copier, an antifouling coat for kitchen, electronic equipment, heat exchange Water- and moisture-proof coatings and anti-soiling coatings such as batteries and batteries, anti-soiling coatings for toiletries, coatings on components that require liquid repellency while conducting, water- and water- and water-sliding coatings of heat exchangers, vibrating sieves and cylinders Etc.
  • front protective plates for liquid crystal displays, organic EL displays, plasma displays, etc. anti-reflection plates, polarizing plates, anti-glare plates, or those with anti-reflection film treatment on their surfaces
  • car navigation systems Car audio, tablet PC, smart phone, wearable terminal, digital camera, portable audio player, mobile phone, touch panel sheet of equipment such as portable information terminal etc.
  • Display input device to operate on the screen with human finger or palm such as touch panel display Having various devices, toilets, baths, washrooms, decorative materials around water such as kitchens, water-repellent and waterproof coats for waterproof coating heat exchangers for wiring boards, water-repellent coatings for solar cells, waterproof and water-repellent for printed wiring boards
  • Waterproof for coats, electronic equipment housings and electronic parts Water coat, insulation improvement coat of power transmission line, waterproof / water repellent coat of various filters, waterproof coat of radio wave absorbing material and sound absorbing material, bath, kitchen equipment, antifouling coat for toiletries, water repellent / waterproof of heat exchanger
  • the surface coating include a slippery coating, a surface low friction coating such as a vibrating screen and the inside of a cylinder, a machine component, a vacuum equipment component, a bearing component, an automobile component, a surface protective coating such as a tool.

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Abstract

Le problème décrit par la présente invention concerne la fourniture d'un nouveau composé contenant du fluor et un procédé de production de celui-ci. La présente invention concerne un composé contenant du fluor représenté par la formule 1, dans laquelle R1 représente un groupe hydrocarboné monovalent ayant de 1 à 6 atomes de carbone, Y1 est un groupe hydrolysable ou Z, R4 est une liaison simple ou un groupe alkylène linéaire ou ramifié ayant de 1 à 6 atomes de carbone, m est un nombre entier de 1 à 3, Z est -R5SiR2 3 -nY2 n, R2 est un groupe hydrocarboné monovalent ayant de 1 à 6 atomes de carbone, Y2 est un groupe hydrolysable, R5 est un groupe alkylène ayant de 1 à 6 atomes de carbone, n est un nombre entier de 1 à 3, et Rf est un polyfluoro qui peut avoir un atome d'oxygène éthérique ayant un poids formulaire de 50 à 10 000, et dans le cas où il y a deux ou plus, R1, R2, R4, R5, Y1, Y2, m, n et Rf peuvent être identiques ou différents.
PCT/JP2018/024656 2017-08-22 2018-06-28 Composé contenant du fluor, composition, solution de revêtement et procédé de production d'un composé contenant du fluor WO2019039083A1 (fr)

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WO2020137998A1 (fr) 2018-12-26 2020-07-02 Ａｇｃ株式会社 Substrat fixé à une couche hydrofuge et oléofuge et procédé pour sa fabrication
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WO2017038830A1 (fr) * 2015-09-01 2017-03-09 旭硝子株式会社 Composé éther fluoré, composition d'éther fluoré, solution de revêtement et élément

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WO2020100759A1 (fr) 2018-11-13 2020-05-22 Ａｇｃ株式会社 Substrat à couche hydrofuge-oléofuge, matériau de dépôt en phase vapeur, et procédé de production d'un substrat à couche hydrofuge-oléofuge
WO2020137998A1 (fr) 2018-12-26 2020-07-02 Ａｇｃ株式会社 Substrat fixé à une couche hydrofuge et oléofuge et procédé pour sa fabrication
CN113966368A (zh) * 2019-06-05 2022-01-21 大金工业株式会社 组合物
WO2022186269A1 (fr) * 2021-03-05 2022-09-09 Ａｇｃ株式会社 Composé éther contenant du fluor, agent de traitement de surface, composition d'éther contenant du fluor, liquide de revêtement, article, procédé de production d'article et composé

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