WO2013146112A1 - Composé silicone à teneur en groupe polyéther fluoré - Google Patents

Composé silicone à teneur en groupe polyéther fluoré Download PDF

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WO2013146112A1
WO2013146112A1 PCT/JP2013/055874 JP2013055874W WO2013146112A1 WO 2013146112 A1 WO2013146112 A1 WO 2013146112A1 JP 2013055874 W JP2013055874 W JP 2013055874W WO 2013146112 A1 WO2013146112 A1 WO 2013146112A1
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group
formula
ocf
fluoropolyether
silicone compound
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PCT/JP2013/055874
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Japanese (ja)
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吉田　知弘
真介 大下
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ダイキン工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • 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 System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the present invention relates to a silicone compound containing a fluoropolyether group, particularly a perfluoropolyether group.
  • the present invention also relates to a surface treatment agent using such a fluoropolyether group-containing silicone compound.
  • fluorine-containing silane compounds can provide excellent water repellency, oil repellency, antifouling properties and the like when used for surface treatment of a substrate.
  • a layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as a surface treatment layer) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. .
  • a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part is known.
  • this surface treatment agent containing a perfluoropolyether group-containing silane compound is applied to a substrate, the hydrolyzable groups bonded to Si atoms are bonded to each other by reacting with the substrate and between the compounds.
  • a treatment layer can be formed.
  • the layer obtained from the surface treatment agent containing a perfluoropolyether group-containing silane compound can exhibit the above-described functions even in a thin film, it is suitable for optical members such as glasses and touch panels that require optical transparency or transparency. It is preferably used.
  • optical members such as glasses and touch panels that require optical transparency or transparency. It is preferably used.
  • a layer obtained from a conventional surface treatment agent containing a perfluoropolyether group-containing silane compound is no longer necessarily sufficient to meet the increasing demand for improved surface slipperiness.
  • a fluoroalkyl group-containing silicone compound having a siloxane skeleton in the molecular main chain and a fluoroalkyl group having 1 to 6 carbon atoms in the molecular side chain is known (see Patent Document 3). thing).
  • a fluoroalkyl group-containing silicone compound has releasability but does not provide water repellency, oil repellency, antifouling property and the like to the substrate.
  • the surface treatment agent used for providing water repellency, oil repellency, antifouling property, etc. it has a divalent perfluoropolyether group and a siloxane skeleton in the molecular main chain, and has a siloxane skeleton.
  • perfluoropolyether group-containing silicone compounds in which Si atoms are linked via a repeating unit of — (CH 2 ) —, and a hydrolyzable group is bonded to the linked Si atoms. (See Patent Documents 4 and 5).
  • a perfluoropolyether group-containing silicone compound is not always satisfactory in terms of surface slipperiness.
  • An object of the present invention is to provide a novel fluoropolyether group-containing silicone compound which can form a layer having water repellency, oil repellency and antifouling properties and high surface slipperiness. Moreover, an object of this invention is to provide the surface treating agent etc. which are obtained using this fluoro polyether group containing silicone compound.
  • a fluoropolyether group-containing silicone compound represented by any one of the following general formulas (I) and (II).
  • R 1 -Rf-X-G 1 -Y-Z ⁇ I) ZY- (G 1 -X-Rf-X) m -G 1 -YZ (II)
  • R 1 is a substituted or unsubstituted methyl group
  • Rf is a group containing a fluoropolyether group
  • X and Y are the same or different divalent organic groups
  • Z is (It is a silyl group containing a decomposable site
  • G 1 is a linear organopolysiloxane group, a group bonded to X or Y at the terminal, and m is 1 or more and 5 or less.)
  • the fluoropolyether group-containing silicone compound of the present invention has a fluoropolyether group (in Rf), an organopolysiloxane group (G 1 ), and a silyl group (Z) containing a hydrolyzable site.
  • the fluoropolyether group (in Rf) contributes to water repellency and oil repellency as well as antifouling properties.
  • the siloxane skeleton of the organopolysiloxane group (G 1 ) contributes to surface slipperiness.
  • the silyl group (Z) containing a hydrolyzable site contributes to friction durability. According to such a fluoropolyether group-containing silicone compound, it becomes possible to form a layer having water repellency, oil repellency, antifouling properties, high surface slipperiness, and friction durability.
  • G 1 represents the following formula: (Wherein R 2 , R 3 , R 4 and R 5 are each independently an alkyl group or an aryl group, and n is 2 or more and 200 or less). .
  • Rf is preferably a group containing a perfluoropolyether group, but part of the fluorine atom may be substituted with a hydrogen atom or another halogen atom. Perfluoropolyether groups can further enhance water and oil repellency and thus antifouling properties.
  • Rf is the following formula: - (R 6) j -R 7 -R 8 - [Wherein R 6 is a perfluoroalkylene group having 1 to 15 carbon atoms, j is 0 or 1, R 7 has the following formula: -(OC 4 F 8 ) v- (OC 3 F 6 ) a- (OC 2 F 4 ) b- (OCF 2 ) c- Wherein a, b, c and v are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and v is at least 1, and each repeating unit enclosed in parentheses Is an arbitrary order in the formula), and a perfluoropolyether group represented by R 8 has the following formula: ⁇ (Q) d ⁇ (CFZ ′′) e ⁇ Wherein Q represents an oxygen atom or a divalent polar group, Z ′′ represents a fluorine atom or a lower fluoroalkyl group, d
  • Rf represents the following formula: —CF 2 CF 2 — (OCF 2 CF 2 CF 2 ) a ′ —OCF 2 CF 2 — (A) (Wherein a ′ is an integer of 1 to 200); or —CF 2 CF 2 — (OCF 2 CF 2 CF 2 ) v ′ — (OCF 2 CF 2 CF 2 ) a ′ — ( OCF 2 CF 2 ) b ' -(OCF 2 ) c' -(B) (Wherein b ′ and c ′ are integers of 1 or more and 200 or less, v ′ and a ′ are integers of 1 or more and 30 or less, and the order of presence of each repeating unit in parentheses is arbitrary in the formula .) It may be a perfluoropolyether group represented by:
  • Z represents the following formula: -SiT x R 9 3-x (Wherein T is a hydroxyl group or a hydrolyzable group, R 9 is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and x is 1, 2 or 3). It may be.
  • X represents the following formula: -(CH 2 ) p -CONH- (CH 2 ) q- , — (CH 2 ) p —NHCO—O— (CH 2 ) q —, or — (CH 2 ) p —O— (CH 2 ) q — (In these formulas, p is an integer of 0 or more and 5 or less, and q is an integer of 1 or more and 20 or less).
  • Y represents the following formula: -(CH 2 ) r -NHCONH- (CH 2 ) s- , — (CH 2 ) r —O—CONH— (CH 2 ) s —, or — (CH 2 ) t — (Wherein r, s and t are each independently an integer of 1 or more and 20 or less).
  • a surface treatment agent comprising the fluoropolyether group-containing silicone compound.
  • the surface treating agent of the present invention contains at least one of the fluoropolyether group-containing silicone compound represented by the general formula (I) and the fluoropolyether group-containing silicone compound represented by the general formula (II), Both of them may be included.
  • Such a surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, and surface slipperiness to a substrate, and is not particularly limited, but is suitable as an antifouling coating agent. Can be used.
  • the surface treating agent of the present invention may further contain a fluoropolyether group-containing silicone compound represented by the following general formula (III).
  • R 1 —Rf—XG 1 —X—Rf—R 1 (III) (Wherein R 1 , Rf, X and G 1 are as described above.)
  • the fluoropolyether group-containing silicone compound represented by the general formula (III) has a fluoropolyether group (in Rf) bonded to an organopolysiloxane group (G 1 ) (via a divalent organic group X). .
  • the fluoropolyether group (in Rf) contributes to water repellency and oil repellency as well as antifouling properties.
  • the siloxane skeleton of the organopolysiloxane group contributes to the surface slipperiness. Therefore, the surface treatment agent further containing the fluoropolyether group-containing silicone compound represented by the general formula (III) imparts higher water repellency, oil repellency, antifouling property, and surface slipperiness to the substrate. Although not particularly limited, it can be suitably used as an antifouling coating agent.
  • an article includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate from the fluoropolyether group-containing silicone compound or the surface treatment agent.
  • the layer in such an article has water repellency, oil repellency, antifouling properties and high surface slipperiness.
  • the article obtained by the present invention is not particularly limited, but may be, for example, an optical member. Optical members are highly demanded to improve surface slipperiness, and the present invention can be suitably used.
  • the substrate can be, for example, glass or transparent plastic.
  • transparent may be anything that can be generally recognized as transparent, but for example, it means a haze value of 3% or less.
  • a novel fluoropolyether group-containing silicone compound which compound has a fluoropolyether group, an organopolysiloxane group, and a silyl group containing a hydrolyzable moiety.
  • a layer having water repellency, oil repellency and antifouling properties, high surface slipperiness, and friction durability can be formed.
  • goods to which they are applied are also provided.
  • Fluoropolyether group-containing silicone compound of the present invention is represented by any one of the following general formulas (I) and (II).
  • R 1 is a substituted or unsubstituted methyl group.
  • substituent for the methyl group include halogen atoms such as fluorine, iodine and bromine.
  • R 1 may be a methyl group substituted with a fluorine atom, and is preferably a trifluoromethyl group (CF 3 —) or a difluoromethyl group (CHF 2 —).
  • Rf is a group containing a fluoropolyether group.
  • the fluoropolyether group of Rf can take a linear, branched or cyclic structure with respect to the ether bond chain, but is preferably linear.
  • the fluoropolyether group of Rf is preferably a perfluoropolyether group, but a part of the fluorine atoms may be substituted with a hydrogen atom or another halogen atom. Furthermore, it is more preferable that Rf is a perfluoropolyether group as a whole.
  • Rf is represented by the following formula: - (R 6) j -R 7 -R 8 - It is preferable that it is group represented by these.
  • R 6 is a perfluoroalkylene group having 1 to 15 carbon atoms (for example, linear or branched), preferably a perfluoroalkylene group having 1 to 2 carbon atoms (—CF 2 —, — C 2 F 4- ).
  • j may be 0 or 1.
  • R 7 represents the following formula: -(OC 4 F 8 ) v- (OC 3 F 6 ) a- (OC 2 F 4 ) b- (OCF 2 ) c- Is a perfluoropolyether group represented by
  • a, b, c and v each represent the number of three types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are independently from 0 to 200, preferably from 1 to 100
  • the sum of a, b, c and v is at least 1, preferably 1 or more and 100 or less.
  • each repeating unit with parentheses a, b, c, and v is described in a specific order in the formula, but the bonding order of these repeating units is limited to this. It is not optional.
  • — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, but preferably — (
  • -(OC 3 F 6 )- is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —.
  • — (OC 2 F 4 ) — may be either — (OCF 2 CF 2 ) — or — (OCF (CF 3 )) —, but is preferably — (OCF 2 CF 2 ) —.
  • R 8 represents the following formula: ⁇ (Q) d ⁇ (CFZ ′′) e ⁇ It is group represented by these.
  • Q represents an oxygen atom (—O—) or another divalent polar group.
  • Rf is a perfluoropolyether group as a whole.
  • the divalent polar group include —O—, —COO—, —OCO—, —CONH—, —COS—, —SCO— and the like, preferably —O—, —COO—, —CONH. -.
  • Z ′′ represents a fluorine atom or a lower fluoroalkyl group, for example, a fluoroalkyl group having 1 to 3 carbon atoms.
  • d and e are each independently an integer of 0 to 50, preferably 0 to 20, and the sum of d and e is at least 1, preferably 1 to 10.
  • the order of existence of each of the repeating units attached with subscripts d and e is described in a specific order in the formula, but the order in which these repeating units are combined is not limited to this, and is arbitrary. It is.
  • Such a compound having a perfluoropolyether group can exhibit excellent water repellency and oil repellency, and thus antifouling properties (for example, preventing adhesion of dirt such as fingerprints).
  • Rf is the following formula: —CF 2 CF 2 — (OCF 2 CF 2 CF 2 ) a ′ —OCF 2 CF 2 — (A) Or —CF 2 CF 2 — (OCF 2 CF 2 CF 2 ) v ′ — (OCF 2 CF 2 CF 2 ) a ′ — (OCF 2 CF 2 ) b ′ — (OCF 2 ) c ′ ⁇ (B) It may be a perfluoropolyether group represented by: In the formula (A), a ′ is an integer of 1 to 200, preferably 1 to 100.
  • b ′ and c ′ are integers of 1 or more and 200 or less
  • v ′ and a ′ are integers of 1 or more and 30 or less
  • the order of presence of each repeating unit enclosed in parentheses is Is optional.
  • the perfluoropolyether group has a linear structure, and can have higher friction durability than the case of having a branched structure, and also has an advantage that synthesis is easy.
  • G 1 is a linear organopolysiloxane group, which is a group bonded to X or Y described later at the terminal (terminal of the linear group). I just need it.
  • the linear organopolysiloxane group can have any suitable organic group in the side chain.
  • a compound having a siloxane skeleton can exhibit excellent surface slipperiness (or lubricity, for example, inconspicuousness such as fingerprints and excellent tactile sensation to fingers).
  • G 1 may be an organopolysiloxane group represented by the following formula:
  • R 2 , R 3 , R 4 and R 5 are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
  • Such substituted or unsubstituted alkyl groups preferably have 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.
  • the substituted or unsubstituted aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • Examples of the substituent of the alkyl group include a halogen atom such as a chlorine atom.
  • Examples of the substituent of the aryl group include a halogen atom such as a chlorine atom, and an alkyl group having 1 to 10 carbon atoms such as a methyl group.
  • R 2 to R 5 include unsubstituted alkyl groups such as methyl, ethyl, propyl, hexyl and dodecyl groups; substituted alkyl groups such as chloromethyl group; unsubstituted aryl such as phenyl and naphthyl groups Groups; substituted aryl groups such as 4-chlorophenyl and 2-methylphenyl groups are included.
  • n is 2 or more and 200 or less, preferably 2 or more and 100 or less. Focusing on only one compound, n is an integer, but the compound of the present invention is a mixture of a plurality of compounds represented by the above general formula (I) or a plurality of compounds represented by the above general formula (II) Where n can be a real number representing the average composition of such a mixture.
  • X is a linking group that bonds between Rf and G 1 (more specifically, Si that forms a siloxane skeleton). X may be a divalent organic group.
  • X is the following formula: -(CH 2 ) p -CONH- (CH 2 ) q- It may be a group represented by In this formula, p is an integer of 0 to 5, preferably 0 to 2, and q is an integer of 1 to 20, preferably 1 to 10. Examples of the group represented by the formula include —CONH—CH 2 CH 2 CH 2 — and the like (provided that the left end of the formula is bonded to Rf and the right end of the formula is bonded to G 1 ).
  • X is the following formula: — (CH 2 ) p —NHCO—O— (CH 2 ) q —, It may be a group represented by In this formula, p is an integer of 0 to 5, preferably 1 to 3, and q is an integer of 1 to 20, preferably 1 to 10. Examples of the group represented by the formula include —CH 2 —NHCO—O—CH 2 CH 2 CH 2 — and the like (provided that the left end of the formula is bonded to Rf and the right end of the formula is G 1 . Shall be combined).
  • X is the following formula: -(CH 2 ) p -O- (CH 2 ) q- It may be a group represented by In this formula, p is an integer of 0 to 5, preferably 1 to 3, and q is an integer of 1 to 20, preferably 1 to 10. Examples of the group represented by the formula include —CH 2 —O—CH 2 CH 2 CH 2 — and the like (where the left end of the formula is bonded to Rf and the right end of the formula is bonded to G 1 ). Shall be.)
  • X is not limited to the above example, and any appropriate divalent organic group can be applied as long as it bonds between Rf and G 1 (more specifically, Si having a siloxane skeleton).
  • Z is a silyl group containing a hydrolyzable moiety. More specifically, Z is the following formula: -SiT x R 9 3-x The silyl group represented by these may be sufficient. In this formula, T and R 9 are groups bonded to Si, and x is 1, 2 or 3. T represents a hydroxyl group or a hydrolyzable group.
  • hydrolyzable groups include —OA, —OCOA, —O—N ⁇ C (A) 2 , —N (A) 2 , —NHA, halogen (wherein A is substituted or unsubstituted Represents an alkyl group having 1 to 3 carbon atoms, and is preferably —OA (alkoxy group).
  • A include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group; and a substituted alkyl group such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
  • R 9 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms (for example, linear or branched), preferably an alkyl group having 1 to 22 carbon atoms, more preferably a linear chain having 1 to 3 carbon atoms. Or a branched alkyl group (CH 3 —, C 2 H 5 —, C 3 H 7 —).
  • the hydrolyzable group (—T) bonded to Si can be bonded by reacting with the base material and between the compounds. Excellent friction durability (relative to oil and fluorine-containing oil).
  • Y is a linking group that bonds between G 1 (more specifically, Si forming a siloxane skeleton) and Z.
  • Y may be a divalent organic group.
  • Y may be the same as X or different.
  • Y represents the following formula: -(CH 2 ) r -NHCONH- (CH 2 ) s- It may be a group represented by In this formula, r and s are each independently an integer of 1 to 20, preferably 1 to 10.
  • Y is the following formula: -(CH 2 ) r -O-CONH- (CH 2 ) s- It may be a group represented by In this formula, r and s are each independently an integer of 1 to 20, preferably 1 to 10.
  • Y is the following formula: -(CH 2 ) t- It may be a group represented by In this formula, t is an integer of 1 to 20, preferably 1 to 10.
  • Y is not limited to the above example, and any appropriate divalent organic group can be applied as long as it bonds between Si and Z forming a siloxane skeleton.
  • m is 1 or more and 5 or less, preferably 1 or more and 3 or less. Focusing on only one compound, m is an integer, but the compound of the present invention may be a mixture of a plurality of compounds represented by the above general formula (II). It can be a real number representing the average composition.
  • the fluoropolyether group-containing silicone compound represented by the general formulas (I) and (II) of the present invention has been described above.
  • the fluoropolyether group-containing silicone compound represented by the general formula (I) preferably has an average molecular weight of, for example, 1000 to 30000.
  • the fluoropolyether group-containing silicone compound represented by the general formula (II) preferably has an average molecular weight of, for example, 2000 to 15000. Thereby, the high solubility with respect to a solvent is acquired, and there exists an advantage that a synthesis
  • “average molecular weight” refers to a number average molecular weight.
  • the fluoropolyether group-containing silicone compound of the present invention can be produced by any appropriate method.
  • the fluoropolyether group-containing silicone compound represented by the general formula (I) is represented by the following general formula (ia): H 2 N— (CH 2 ) q ′ -G 1- (CH 2 ) r ′ —NH 2 ...
  • X represents the following formula: -(CH 2 ) p -CONH- (CH 2 ) q- (Wherein p and q are as described above, the left end of the formula is bonded to Rf, and the right end of the formula is bonded to G 1 ), and Y is the following formula: -(CH 2 ) r -NHCONH- (CH 2 ) s- (Wherein, r and s are as described above, and the left end of the formula is bonded to G 1 and the right end of the formula is bonded to Z).
  • R 1 —Rf—XG 1 —X—Rf—R 1 (III) (Wherein R 1 , Rf, X and G 1 are as described above) can be produced as a by-product.
  • X represents the following formula: — (CH 2 ) p —CONH— (CH 2 ) q —, or — (CH 2 ) p —O—CONH— (CH 2 ) q — (Wherein p and q are as described above, the left end of the formula is bonded to Rf, and the right end of the formula is bonded to G 1 ).
  • the fluoropolyether group-containing silicone compound represented by the general formula (I) is represented by the following general formula (ii-a): HO— (CH 2 ) q ′ —G 1 — (CH 2 ) r ′ —OH (ii-a)
  • G 1 is as described above
  • q ′ and r ′ are each independently an integer of 1 to 20, and typically q ′ and r ′ may be the same.
  • X represents the following formula: — (CH 2 ) p —NHCO—O— (CH 2 ) q ⁇ (Wherein p and q are as described above, the left end of the formula is bonded to Rf, and the right end of the formula is bonded to G 1 ), and Y is the following formula: -(CH 2 ) r -O-CONH- (CH 2 ) s- (Wherein, r and s are as described above, and the left end of the formula is bonded to G 1 and the right end of the formula is bonded to Z).
  • the fluoropolyether group-containing silicone compound represented by the general formula (I) is represented by the following general formula (iii-a): H-G 1- (CH 2 ) t -Z (iii-a) (Wherein G 1 , Z and t are as defined above), the compound represented by the following general formula (iii-b): R 1 —Rf— (CH 2 ) p —O— (CH 2 ) q ⁇ 2 —CH ⁇ CH 2 (iii) -b (Wherein R 1 , Rf, p and q are as described above, but q is 2 or more in this example) and can be obtained by subjecting to a hydrosilylation reaction.
  • X represents the following formula: -(CH 2 ) p -O- (CH 2 ) q- (Wherein p and q are as described above, the left end of the formula is bonded to Rf, and the right end of the formula is bonded to G 1 ), and Y is the following formula: -(CH 2 ) t- (Wherein t is as described above).
  • the fluoropolyether group-containing silicone compound represented by the general formula (II) is represented by the following general formula (ia): H 2 N— (CH 2 ) q ′ -G 1- (CH 2 ) r ′ —NH 2 ...
  • X represents the following formula: -(CH 2 ) p -CONH- (CH 2 ) q- (Wherein p and q are as described above, the left end of the formula is bonded to Rf, and the right end of the formula is bonded to G 1 ), and Y is the following formula: -(CH 2 ) r -NHCONH- (CH 2 ) s- (Wherein, r and s are as described above, and the left end of the formula is bonded to G 1 and the right end of the formula is bonded to Z).
  • the fluoropolyether group-containing silicone compound represented by the general formula (II) is represented by the following general formula (ii-a): HO— (CH 2 ) q ′ —G 1 — (CH 2 ) r ′ —OH (ii-a)
  • G 1 is as described above
  • q ′ and r ′ are each independently an integer of 1 to 20, and typically q ′ and r ′ may be the same.
  • the following general formula (ii-c) OCN- (CH 2 ) s -Z (ii-c) (Wherein Z and s are as described above) and can be obtained by subjecting the compound to a
  • X represents the following formula: — (CH 2 ) p —NHCO—O— (CH 2 ) q ⁇ (Wherein p and q are as described above, the left end of the formula is bonded to Rf, and the right end of the formula is bonded to G 1 ), and Y is the following formula: -(CH 2 ) r -O-CONH- (CH 2 ) s- (Wherein, r and s are as described above, and the left end of the formula is bonded to G 1 and the right end of the formula is bonded to Z).
  • the fluoropolyether group-containing silicone compound represented by the general formula (II) is represented by the following general formula (iii-a): H-G 1- (CH 2 ) t -Z (iii-a) (Wherein G 1 , Z and t are as defined above), a compound represented by the following general formula (iii-b ′): CH 2 ⁇ CH— (CH 2 ) q-2 —O— (CH 2 ) p —Rf— (CH 2 ) p —O— (CH 2 ) q-2 —CH ⁇ CH 2 ...
  • X represents the following formula: -(CH 2 ) p -O- (CH 2 ) q- (Wherein p and q are as described above, the left end of the formula is bonded to Rf, and the right end of the formula is bonded to G 1 ), and Y is the following formula: -(CH 2 ) t- (Wherein t is as described above, the left end of the formula is bonded to G 1 , and the right end of the formula is bonded to Z).
  • a raw material in which a compound represented by the general formula (ib) and a compound represented by the general formula (ib ′) are mixed, or a compound represented by the general formula (ii-b) And a compound represented by general formula (iii-b ′), a compound represented by general formula (iii-b) and a compound represented by general formula (iii-b ′) May be used (in these raw materials, a fluorine-containing oil represented by the general formula R 1 -Rf-F described later may be further mixed).
  • the fluoropolyether group-containing silicone compound represented by the general formula (I) and the fluoropolyether group-containing silicone compound represented by the general formula (II) are mixed. Will be.
  • the fluoropolyether group-containing silicone compound represented by the general formula (III) and other various by-products may be present.
  • any of the above amide bond forming reaction, urea bond forming reaction, urethane bond forming reaction and hydrosilylation reaction may proceed without solvent or in a solvent.
  • solvents include perfluoroaliphatic hydrocarbons, aromatic hydrocarbons having fluorine-containing substituents (eg, bis (trifluoromethyl) benzene), hydrofluoroethers, and the like, alone or Two or more kinds may be used in combination.
  • the amide bond forming reaction and the urea bond forming reaction can be carried out in the absence of a catalyst or in the presence of any appropriate catalyst, for example, at 20 to 130 ° C., conveniently under normal pressure.
  • a perfluoropolyether compound dropwise to the silicone compound from the viewpoint of suppressing the generation of by-products.
  • the urethane bond formation reaction can be carried out in the absence of a catalyst or in the presence of a catalyst such as dibutyltin dilaurate, for example, at 20 to 130 ° C., conveniently under normal pressure.
  • a catalyst such as dibutyltin dilaurate, for example, at 20 to 130 ° C., conveniently under normal pressure.
  • it is preferable to react under a nitrogen stream from the viewpoint of suppressing the condensation reaction.
  • the hydrosilylation reaction can be carried out in the presence of a catalyst such as platinum, for example, at 0 to 130 ° C., conveniently under normal pressure.
  • a catalyst such as platinum, for example, at 0 to 130 ° C., conveniently under normal pressure.
  • the compound of the present invention is useful in a surface treatment agent as described below, but is not limited thereto, and can be used as, for example, a lubricant or a compatibilizing agent.
  • the surface treatment agent (or surface treatment composition) of this invention should just contain the fluoro polyether group containing silicone compound of this invention mentioned above. That is, at least one of the fluoropolyether group-containing silicone compound represented by the general formula (I) and the fluoropolyether group-containing silicone compound represented by the general formula (II) is included, and both of these are included. Also good. When these are used in combination, the compound represented by the general formula (I) and the compound represented by the general formula (II) may exist, for example, in a mass ratio of 100: 1 to 2: 1. It is not limited to.
  • the surface treatment agent only needs to contain a fluoropolyether group-containing silicone compound as a main component or an active ingredient.
  • the “main component” means a component having a content in the surface treatment agent exceeding 50%, and the “active ingredient” is formed on the substrate to be surface-treated to form a surface treatment layer, It means a component that can express some function (water repellency, oil repellency, antifouling property, surface slipperiness, friction durability, etc.).
  • the surface treatment agent of the present invention contains the above-mentioned fluoropolyether group-containing silicone compound, has water repellency, oil repellency, antifouling properties, has high surface slipperiness, and has friction durability. Since the surface treatment layer can be formed, it is suitably used as an antifouling coating agent.
  • the surface treating agent of the present invention may contain a fluoropolyether group-containing silicone compound represented by the following general formula (III).
  • R 1 —Rf—XG 1 —X—Rf—R 1 (III) (Wherein R 1 , Rf, X and G 1 are as described above.)
  • the fluoropolyether group-containing silicone compound represented by the general formula (III) is converted into an organopolysiloxane group (G 1 ) (more specifically, a Si atom forming a siloxane skeleton) (via a divalent organic group X).
  • the fluoropolyether group (in Rf) contributes to water repellency and oil repellency as well as antifouling properties. Further, the siloxane skeleton of the organopolysiloxane group contributes to the surface slipperiness.
  • the group-containing silicone compound can be contained, for example, in an amount of 0 to 80 parts by mass, preferably 0 to 40 parts by mass.
  • the surface treating agent of the present invention can be understood as a silicone oil (for example, non-fluorine type) silicone compound (hereinafter referred to as “silicone oil” for the purpose of distinguishing from the fluoropolyether group-containing silicone compound of the present invention). May be included. Silicone oil contributes to further improving the surface slipperiness of the surface treatment layer.
  • silicone oil for example, non-fluorine type silicone compound
  • the silicone oil is, for example, 0 to 80 parts by mass, preferably 100 parts by mass with respect to 100 parts by mass in total of the fluoropolyether group-containing silicone compounds represented by the general formulas (I) and (II). 0 to 40 parts by weight may be included.
  • a silicone oil for example, a linear or cyclic silicone oil having a siloxane bond of 2000 or less can be used.
  • the linear silicone oil may be so-called straight silicone oil and modified silicone oil.
  • the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil.
  • modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
  • the cyclic silicone oil include cyclic dimethylsiloxane oil.
  • the surface treatment agent of the present invention may contain a fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoropolyether compound (hereinafter, distinguished from the fluoropolyether group-containing silicone compound of the present invention).
  • a fluorine-containing oil preferably a perfluoropolyether compound (hereinafter, distinguished from the fluoropolyether group-containing silicone compound of the present invention).
  • fluorinated oil a perfluoropolyether compound
  • the fluorine-containing oil is, for example, 0 to 80 parts by mass, preferably 100 parts by mass of the fluoropolyether group-containing silicone compounds represented by the general formulas (I) and (II). May be included at 0 to 40 parts by weight.
  • fluorine-containing oils examples include compounds represented by the following general formula (IV) (perfluoropolyether compounds).
  • R 21 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, and preferably an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms is preferably a perfluoroalkyl group having 1 to 16 carbon atoms, more preferably 1 carbon atom.
  • R 22 represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, preferably an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms is preferably a perfluoroalkyl group having 1 to 16 carbon atoms, more preferably 1 carbon atom.
  • a ′′, b ′′, c ′′ and v ′′ each represent the number of three types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, each independently an integer of 0 to 300 Wherein the sum of a ′′, b ′′, c ′′ and v ′′ is at least 1, preferably 1-100.
  • the order of presence of each repeating unit with subscripts a ′′, b ′′, c ′′, v ′′ and enclosed in parentheses is arbitrary in the formula.
  • — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, preferably- (OCF 2 CF 2 CF 2 CF 2 ) —.
  • — (OCF 2 CF 2 ) — is preferable.
  • — (OC 2 F 4 ) — may be either — (OCF 2 CF 2 ) — or — (OCF (CF 3 )) —, but is preferably — (OCF 2 CF 2 ) —.
  • the perfluoropolyether compound represented by the above general formula (IV) may be a compound represented by any of the following general formulas (IVa) and (IVb) (one kind or a mixture of two or more kinds).
  • R 21 and R 22 are as described above.
  • a ′ ′′ is an integer of 1 or more and 100 or less.
  • a ′ ′′ and v ′ ′′ are each independently an integer of 1 to 30, and b ′ ′′ and c ′ ′′ are each independently an integer of 1 to 300.
  • the order of presence of each repeating unit in parentheses with subscripts a ′ ′′, b ′ ′′, c ′ ′′ or v ′ ′′ is arbitrary in the formula.
  • the compound represented by the general formula (IVa) and the compound represented by the general formula (IVb) may be used alone or in combination. It is preferable to use the compound represented by the general formula (IVb) rather than the compound represented by the general formula (IVa) because higher surface slip properties can be obtained. When these are used in combination, it is preferable to use the compound represented by the general formula (IVa) and the compound represented by the general formula (IVb) at a mass ratio of 1: 1 to 1:30. According to such a mass ratio, a surface treating agent having an excellent balance between surface slipperiness and friction durability can be obtained.
  • the fluorine-containing oil is represented by the general formula R 1 -Rf-F (wherein R 1 and Rf are as described above, and R 1 is preferably a trifluoromethyl group). It may be a compound.
  • the compound represented by R 1 -Rf-F is preferred in that high affinity is obtained with each compound represented by the above general formulas (I) and (II).
  • the fluorine-containing oil preferably has an average molecular weight of 1000 to 30000. Thereby, high surface slipperiness can be obtained.
  • it preferably has an average molecular weight of 2000 to 6000, and in the case of the compound represented by the general formula (IVb), 8000 to 30000 It is preferable to have an average molecular weight of In the range of these average molecular weights, high surface slipperiness can be obtained.
  • the surface treatment agent of the present invention may contain a perfluoropolyether group-containing silane compound.
  • the perfluoropolyether group-containing silane compound contributes to the water repellency, oil repellency, antifouling property, surface slipperiness and friction durability of the surface treatment layer, and can contribute to improvement of friction durability.
  • the perfluoropolyether group-containing silane compound is, for example, from 0 to about 100 parts by mass of the fluoropolyether group-containing silicone compounds represented by the general formulas (I) and (II). It can be included at 80 parts by weight, preferably 0-40 parts by weight.
  • Examples of such a perfluoropolyether group-containing silane compound include compounds represented by any one of the following general formulas (Va) and (Vb) (may be one kind or a mixture of two or more kinds).
  • R 31 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, and preferably an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms is preferably a perfluoroalkyl group having 1 to 16 carbon atoms, more preferably 1 carbon atom. To 3 perfluoroalkyl groups.
  • a, b, c and v each represent the number of three types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 200, and a, b, c And the sum of v is at least 1, preferably 1-100.
  • the order of presence of each repeating unit with subscripts a, b, c, and v enclosed in parentheses is arbitrary in the formula.
  • — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, preferably- (OCF 2 CF 2 CF 2 CF 2 ) —.
  • — (OCF 2 CF 2 ) — is preferable.
  • — (OC 2 F 4 ) — may be either — (OCF 2 CF 2 ) — or — (OCF (CF 3 )) —, but is preferably — (OCF 2 CF 2 ) —.
  • k is 0 or 1.
  • f is an integer of 1 or more and 10 or less.
  • g is an integer of 0 or more and 2 or less.
  • X ′ represents a hydrogen atom or a halogen atom.
  • the halogen atom is preferably an iodine atom, a chlorine atom, or a fluorine atom.
  • Y ′ represents a hydrogen atom or a lower alkyl group.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms.
  • Z ′ represents a fluorine atom or a lower fluoroalkyl group.
  • the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably a trifluoromethyl group. It is.
  • T ′ and R 32 are groups bonded to Si.
  • T ′ represents a hydroxyl group or a hydrolyzable group.
  • hydrolyzable groups include —OA, —OCOA, —O—N ⁇ C (A) 2 , —N (A) 2 , —NHA, halogen (wherein A is substituted or unsubstituted Represents an alkyl group having 1 to 3 carbon atoms).
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
  • R 32 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
  • x is 1, 2 or 3.
  • there are a plurality of X ′, Y ′, Z ′, T ′, R 32 , k, f, g, and x but they may be the same or different.
  • perfluoropolyether group-containing silane compound is a compound represented by any one of the following general formulas (VIa) and (VIb) (which may be one or a mixture of two or more). It is done.
  • R 31 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, and preferably an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms is preferably a perfluoroalkyl group having 1 to 16 carbon atoms, more preferably 1 carbon atom. To 3 perfluoroalkyl groups.
  • a, b, c and v each represent the number of three types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 200, and a, b, c And the sum of v is at least 1, preferably 1-100.
  • the order of presence of each repeating unit with subscripts a, b, c, and v enclosed in parentheses is arbitrary in the formula.
  • — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, preferably- (OCF 2 CF 2 CF 2 CF 2 ) —.
  • — (OCF 2 CF 2 ) — is preferable.
  • — (OC 2 F 4 ) — may be either — (OCF 2 CF 2 ) — or — (OCF (CF 3 )) —, but is preferably — (OCF 2 CF 2 ) —.
  • k is 0 or 1.
  • h is 1 or 2.
  • i is an integer of 2 or more and 20 or less.
  • Z ′ represents a fluorine atom or a lower fluoroalkyl group.
  • the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably a trifluoromethyl group. It is.
  • T ′ and R 32 are groups bonded to Si.
  • T ′ represents a hydroxyl group or a hydrolyzable group.
  • hydrolyzable groups include —OA, —OCOA, —O—N ⁇ C (A) 2 , —N (A) 2 , —NHA, halogen (wherein A is substituted or unsubstituted Represents an alkyl group having 1 to 3 carbon atoms).
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
  • R 32 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms.
  • x is 1, 0 or 3. In the formula, there are a plurality of Z ′, T ′, R 32 , k, h, i, and x, but they may be the same or different.
  • the molecular weight of the perfluoropolyether group-containing silane compound is not particularly limited, but may have an average molecular weight of, for example, 1000 to 12000. Among these ranges, an average molecular weight of 2000 to 10,000 is preferable from the viewpoints of water repellency, oil repellency, surface slipperiness (for example, fingerprint wiping properties) and friction durability.
  • the surface treatment agent of the present invention comprises a compound that is non-reactive with a substrate (for example, a fluoropolyether group-containing silicone compound represented by the general formula (III), silicone oil, and / or fluorine-containing oil), Both perfluoropolyether group-containing silane compounds may be included.
  • a substrate for example, a fluoropolyether group-containing silicone compound represented by the general formula (III), silicone oil, and / or fluorine-containing oil
  • Both perfluoropolyether group-containing silane compounds may be included.
  • the surface treatment agent of the present invention is non-reactive with respect to the base material with respect to 100 parts by mass of the fluoropolyether group-containing silicone compounds represented by the general formulas (I) and (II).
  • the compound may be contained, for example, in an amount of 0 to 80 parts by mass, preferably 0 to 40 parts by mass, and the perfluoropolyether group-containing silane compound may be contained in an amount of, for example, 0 to 80 parts by mass, preferably 0 to 40 parts by mass. .
  • the article of the present invention comprises a substrate and a fluoropolyether group-containing silicone compound represented by the above general formula (I) and / or (II) on the surface of the substrate or a surface treatment agent (hereinafter, these are representatives). And a layer (surface treatment layer) formed from a surface treatment agent).
  • This article can be manufactured, for example, as follows.
  • the substrate that can be used in the present invention is, for example, glass, resin (natural or synthetic resin, for example, a general plastic material, plate, film, or other forms), metal (aluminum, copper May be a single metal such as iron or a composite of an alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc. It can be made of any material.
  • the material constituting the surface of the substrate may be an optical member material such as glass or transparent plastic.
  • some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate.
  • the antireflection layer either a single-layer antireflection layer or a multilayer antireflection layer may be used.
  • inorganic materials that can be used for the antireflection layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 , MgO.
  • the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the substrate (glass). It may be.
  • ITO indium tin oxide
  • the base material is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, And a liquid crystal display module or the like.
  • the shape of the substrate is not particularly limited.
  • the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.
  • a base material at least a surface portion thereof may be made of a material originally having a hydroxyl group.
  • materials include glass, and metals (particularly base metals) on which a natural oxide film or a thermal oxide film is formed on the surface, ceramics, and semiconductors.
  • it can be introduced to the surface of the substrate by applying some pretreatment to the substrate. Or increase it. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation.
  • the plasma treatment can be preferably used for introducing or increasing hydroxyl groups on the surface of the base material and for cleaning the base material surface (removing foreign matter or the like).
  • an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously formed in the form of a monomolecular film on the substrate surface by the LB method (Langmuir-Blodgett method) or chemical adsorption method. And then cleaving the unsaturated bond in an atmosphere containing oxygen, nitrogen or the like.
  • the substrate may be made of a material containing at least a surface portion of a silicone compound having one or more other reactive groups, for example, Si—H groups, or an alkoxysilane.
  • a film of the surface treatment agent is formed on the surface of the base material, and the film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent.
  • the film formation of the surface treatment agent can be carried out by applying the surface treatment agent to the surface of the substrate so as to cover the surface.
  • the coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.
  • wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
  • dry coating methods include vacuum deposition, sputtering, CVD, and similar methods.
  • vacuum deposition method include resistance heating, electron beam, high frequency heating, ion beam, and similar methods.
  • CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods.
  • the surface treatment agent can be diluted with a solvent and then applied to the substrate surface.
  • the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane and perfluoro -1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons; hydrofluoroethers (HFE) (eg perfluoropropylmethyl ether (C 3 F 7 OCH 3 ), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ), perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ), perfluorohexyl methyl ether (C 2 F 5 CF (OCH
  • Kill ether perfluoroalkyl group and the alkyl group may be linear or branched
  • These solvents can be used alone or as a mixture of two or more.
  • perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) and / or hydrofluoroether is preferable, and perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) is particularly preferable.
  • the film formation is preferably carried out so that the surface treatment agent is present in the film together with a catalyst for hydrolysis and dehydration condensation.
  • a catalyst for hydrolysis and dehydration condensation.
  • the catalyst may be added to the diluted solution of the surface treatment agent immediately before application to the substrate surface.
  • the surface treatment agent added with a catalyst is vacuum-deposited as it is, or a vacuum is formed using a pellet-like material obtained by impregnating a surface treatment agent added with a catalyst into a porous metal such as iron or copper. A vapor deposition process may be performed.
  • any suitable acid or base can be used for the catalyst.
  • the acid catalyst for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used.
  • a base catalyst ammonia, organic amines, etc. can be used, for example.
  • the membrane is post-treated as necessary.
  • this post-processing is not specifically limited, For example, a water supply and drying heating may be implemented sequentially, and it may be implemented as follows in detail.
  • all of T contained in Z is a hydroxyl group (and when present, the above general formulas (Va), (Vb)
  • T ′ is all a hydroxyl group), it is not always necessary to supply water.
  • moisture is supplied to this film (hereinafter also referred to as a precursor film).
  • the method for supplying moisture is not particularly limited, and for example, methods such as dew condensation due to a temperature difference between the precursor film (and the substrate) and the surrounding atmosphere, or spraying of steam (steam) may be used.
  • the fluoropolyether group-containing silicone compound represented by the general formula (I) and / or (II) in the surface treatment agent (and perfluoropolyether, if present) It is considered that water acts on the hydrolyzable group bonded to Si of the group-containing silane compound), and the compound can be rapidly hydrolyzed.
  • the water supply can be performed in an atmosphere of 0 to 500 ° C., preferably 100 ° C. or higher and 300 ° C. or lower, for example. By supplying moisture in such a temperature range, hydrolysis can be advanced. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.
  • the precursor film is heated on the surface of the substrate in a dry atmosphere exceeding 60 ° C.
  • the drying heating method is not particularly limited, and the temperature of the precursor film together with the base material is over 60 ° C., preferably over 100 ° C., for example, 500 ° C. or less, preferably 300 ° C. or less, and What is necessary is just to arrange
  • the pressure at this time is not specifically limited, it can be simply a normal pressure.
  • a hydropolyether group-containing silicone compound represented by the general formula (I) and / or (II) (and a perfluoropolyether group-containing silane compound, if present) is not hydrolyzed.
  • a group bonded to Si after decomposition in the compound represented by any one of the general formulas (I) and (II), when all of T contained in Z is a hydroxyl group, this is the hydroxyl group.
  • between such a compound and a base material it reacts rapidly between the group couple
  • the reactive group is a hydroxyl group
  • dehydration condensation is performed.
  • the fluoropolyether group-containing silicone compound, silicone oil and / or fluorine-containing oil represented by the general formula (III) are mixed.
  • the above water supply and drying heating may be continuously performed by using superheated steam.
  • Superheated steam is a gas obtained by heating saturated steam to a temperature higher than the boiling point, and exceeds 100 ° C. under normal pressure, generally 500 ° C. or lower, for example, 300 ° C. or lower, and has a boiling point. It is a gas that has become an unsaturated water vapor pressure by heating to a temperature exceeding.
  • dew condensation occurs on the surface of the precursor film due to the temperature difference between the superheated water vapor and the relatively low temperature precursor film. Moisture is supplied to the membrane.
  • the moisture on the surface of the precursor film is vaporized in a dry atmosphere by the superheated steam, and the moisture content on the surface of the precursor film gradually decreases. While the amount of moisture on the surface of the precursor film is reduced, that is, while the precursor film is in a dry atmosphere, the precursor film on the surface of the substrate comes into contact with the superheated steam, thereby the temperature of the superheated steam ( It will be heated to a temperature exceeding 100 ° C. under normal pressure. Therefore, if superheated steam is used, moisture supply and drying heating can be carried out continuously only by exposing the substrate on which the precursor film is formed to superheated steam.
  • Post-processing can be performed as described above. It should be noted that such post-treatment can be performed to further improve friction durability, but is not essential for producing the articles of the present invention. For example, after applying the surface treatment agent to the substrate surface, it may be left still.
  • the surface treatment layer derived from the film of the surface treatment agent is formed on the surface of the base material, and the article of the present invention is manufactured.
  • the surface treatment layer thus obtained has water repellency, oil repellency, antifouling properties (for example, preventing adhesion of dirt such as fingerprints), surface slipperiness (or lubricity, for example, wiping of dirt such as fingerprints, finger Excellent tactile sensation), friction durability, and the like, and can be suitably used as a functional thin film.
  • the article having the surface treatment layer obtained thereby is not particularly limited, but may be an optical member.
  • optical members include: lenses such as eyeglasses; front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDP and LCD; for devices such as mobile phones and portable information terminals. Touch panel sheet; disc surface of an optical disc such as a Blu-ray disc, DVD disc, CD-R, or MO; optical fiber or the like.
  • the thickness of the surface treatment layer is not particularly limited.
  • the thickness of the surface treatment layer is preferably in the range of 1 to 30 nm, preferably 1 to 15 nm, from the viewpoints of optical performance, surface slipperiness, friction durability, and antifouling properties.
  • the articles obtained using the surface treating agent of the present invention have been described in detail.
  • the use of the surface treating agent of the present invention, the method of use or the method of manufacturing the article are not limited to those exemplified above.
  • Example 5 As Examples 1 to 5, a mixture of fluoropolyether group-containing silicone compounds was synthesized in the following Synthesis Examples 1 to 5, respectively, and a surface treatment agent was prepared using each mixture obtained from these. A treatment layer was formed.
  • Pt catalyst
  • Each surface treatment agent prepared above was vacuum-deposited on a slide glass.
  • the processing conditions for vacuum deposition were a pressure of 3.0 ⁇ 10 ⁇ 3 Pa, and 1 mg of each surface treatment agent was deposited per slide glass. Thereafter, the slide glass with the deposited film was left for 24 hours in an atmosphere of a temperature of 20 ° C. and a humidity of 65%. Thereby, a vapor deposition film hardened and a surface treatment layer was formed.
  • Control compound 1 Me 3 SiO- (Me 2 SiO) 13 - (MeHSiO) 13 -SiMe 3
  • Control compound 2 CF 3 CF 2 CF 2 (CF 2 CF 2 CF 2 O) 20 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 3 ⁇
  • Composition 1 A composition comprising Control Compound 1 and Control Compound 2 mixed at a mass ratio of 1: 1.
  • a dynamic friction coefficient ( ⁇ ) was measured in accordance with ASTM D1894 using a surface property measuring machine (“Tribogear TYPE: 14FW”, manufactured by Shinto Kagaku Co., Ltd.) and using a steel ball as a friction element.
  • Oil-based ink wiping off Oil-based ink is applied to the surface of the surface treatment layer using an oil-based marking pen (Zebra Co., Ltd., "Hi-Mackey” (registered trademark)), and this is made of pulp waste (Nippon Paper Crecia Co., Ltd., "Kimwipe” (registered) (Trademark))) (wiping the waste cloth to the treated surface by hand and sliding it in one direction), and wiping performance (easiness of wiping) of the oil-based ink was visually evaluated according to the following index.
  • C About half of the ink remains in one wiping operation.
  • D Ink in one wiping operation. Can not wipe off at all
  • Examples 1 to 5 using the fluoropolyether group-containing silicone compound of the present invention the kinetic friction is as small as in Comparative Example 1 using the control compound 1 (polyorganosilicone compound). A coefficient (high surface slipperiness) and excellent use feeling with a finger are obtained, and water and oil repellency (high) is high enough to be comparable to Comparative Example 2 using Control Compound 2 (perfluoropolyether group-containing silane compound). Contact angle) and excellent oil-based ink wiping properties were obtained. Examples 1 to 5 using the fluoropolyether group-containing silicone compound of the present invention have higher water and oil repellency (contact angle) than Comparative Example 3 using the composition 1 in which the control compounds 1 and 2 are simply mixed. Was large), the coefficient of dynamic friction was small (high surface slipperiness), and the oil-based ink wiping property and the feeling of use with a finger were excellent.
  • the present invention can be suitably used for forming a surface treatment layer on the surface of a variety of substrates, particularly optical members that require transparency.

Abstract

La présente invention concerne un composé silicone à teneur en groupe polyéther fluoré, qui est représenté par la formule générale (I) ou (II). R1-Rf-X-G1-Y-Z (I) Z-Y-(G1-X-Rf-X)m-G1-Y-Z (II) (Dans les formules, R1 représente un groupe méthyle substitué ou non substitué ; Rf représente un groupe qui contient un groupe polyéther fluoré ; X et Y représentent des groupes organiques divalents qui sont identiques ou différents l'un de l'autre ; Z représente un groupe silyle qui contient une fraction hydrolysable ; G1 représente un groupe organopolysiloxane linéaire qui est lié à X ou Y à une extrémité ; et m représente un nombre de 1 à 5 (inclus)). Le composé de la présente invention est apte à former une couche qui a un caractère hydrophobe, un caractère oléophobe et des propriétés anti-encrassement, tout en ayant un pouvoir lubrifiant de surface élevé.
PCT/JP2013/055874 2012-03-30 2013-03-04 Composé silicone à teneur en groupe polyéther fluoré WO2013146112A1 (fr)

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WO2018047695A1 (fr) * 2016-09-08 2018-03-15 ダイキン工業株式会社 Composition contenant un composé silane contenant un groupe perfluoro(poly)éther
US9957359B2 (en) 2014-03-28 2018-05-01 Dow Corning Corporation Fluorinated copolymer compositions and associated methods, uses and articles
US10544260B2 (en) 2017-08-30 2020-01-28 Ppg Industries Ohio, Inc. Fluoropolymers, methods of preparing fluoropolymers, and coating compositions containing fluoropolymers
EP3950774A1 (fr) * 2020-08-03 2022-02-09 Shin-Etsu Chemical Co., Ltd. Composé perfluoropolyéther modifié par une amine diterminale et sa préparation et composition repoussant les liquides, produit durci et substrat revêtu le contenant
EP3950773A1 (fr) * 2020-08-03 2022-02-09 Shin-Etsu Chemical Co., Ltd. Composé de perfluoropolyéther modifié par silanole de façon diterminale et sa préparation
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WO2014069592A1 (fr) * 2012-11-05 2014-05-08 ダイキン工業株式会社 Composé de type silane contenant un groupe perfluoro(poly)éther
US10563070B2 (en) 2012-11-05 2020-02-18 Daikin Industries, Ltd. Silane compound containing perfluoro(poly)ether group
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US9957359B2 (en) 2014-03-28 2018-05-01 Dow Corning Corporation Fluorinated copolymer compositions and associated methods, uses and articles
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WO2018047695A1 (fr) * 2016-09-08 2018-03-15 ダイキン工業株式会社 Composition contenant un composé silane contenant un groupe perfluoro(poly)éther
US10544260B2 (en) 2017-08-30 2020-01-28 Ppg Industries Ohio, Inc. Fluoropolymers, methods of preparing fluoropolymers, and coating compositions containing fluoropolymers
EP3950774A1 (fr) * 2020-08-03 2022-02-09 Shin-Etsu Chemical Co., Ltd. Composé perfluoropolyéther modifié par une amine diterminale et sa préparation et composition repoussant les liquides, produit durci et substrat revêtu le contenant
EP3950773A1 (fr) * 2020-08-03 2022-02-09 Shin-Etsu Chemical Co., Ltd. Composé de perfluoropolyéther modifié par silanole de façon diterminale et sa préparation
CN116724094A (zh) * 2021-01-19 2023-09-08 大金工业株式会社 表面处理剂
CN116507682A (zh) * 2021-01-28 2023-07-28 大金工业株式会社 表面处理用液态组合物

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