WO2013172177A1 - Composé de type silicone contenant un groupe fluoropolyéther - Google Patents

Composé de type silicone contenant un groupe fluoropolyéther Download PDF

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Publication number
WO2013172177A1
WO2013172177A1 PCT/JP2013/062271 JP2013062271W WO2013172177A1 WO 2013172177 A1 WO2013172177 A1 WO 2013172177A1 JP 2013062271 W JP2013062271 W JP 2013062271W WO 2013172177 A1 WO2013172177 A1 WO 2013172177A1
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group
formula
fluoropolyether
silicone compound
containing silicone
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PCT/JP2013/062271
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English (en)
Japanese (ja)
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吉田　知弘
健介 茂原
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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
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups

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 having a structure represented by any of the following general formulas (Ia), (Ib), (IIa) and (IIb).
  • R 1 is a substituted or unsubstituted methyl group
  • Rf is a group containing a fluoropolyether group
  • X is a trivalent organic group
  • Y is a divalent organic group
  • Z is a silyl group containing a hydrolyzable site
  • S 1 is a monovalent organopolysiloxane group
  • S 2 is a divalent organopolysiloxane group
  • m is 1 or more and 5 or less.
  • the fluoropolyether group-containing silicone compound of the present invention comprises a fluoropolyether group (in Rf), an organopolysiloxane group (S 1 or S 2 ), 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 (S 1 or S 2 ) 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.
  • S 1 represents the following formula: (In the formula, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently an alkyl group or an aryl group, and n is 1 or more and 200 or less.) It may be an organopolysiloxane group represented by:
  • S 2 represents the following formula: (In the formula, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently an alkyl group or an aryl group, and n is 1 or more and 200 or less.) It may be an organopolysiloxane group represented by:
  • Rf is preferably a group containing a perfluoropolyether group, but a part of the fluorine atoms are hydrogen atoms or other halogen atoms. May be substituted. Perfluoropolyether groups can further enhance water and oil repellency and thus antifouling properties.
  • Rf is the following formula: - (R 9) j -R 10 -R 11 - [Wherein R 9 is a perfluoroalkylene group having 1 to 15 carbon atoms, j is 0 or 1, R 10 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 The order of presence of is arbitrary in the formula.) A perfluoropolyether group represented by R 11 has the following formula: -(Q) d- (CFZ ') e- (In the formula, Q represents an oxygen atom or a divalent polar group, Z ′ represents a fluorine atom or a lower fluoroalkyl group,
  • Rf represents the following formula: —CF 2 CF 2 — (OCF 2 CF 2 CF 2 ) a ′ —OCF 2 CF 2 — (Wherein, a ′ is an integer of 1 to 200)
  • a ′ is an integer of 1 to 200
  • Z represents the following formula: -SiT x R 12 3-x
  • T is a hydroxyl group or a hydrolyzable group
  • R 12 is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms
  • x is 1, 2 or 3.
  • the silyl group represented by these may be sufficient.
  • X is any one of the following formulas: (In these formulas, p is an integer of 1 to 10, R 13 is a divalent organic group, the left end of the formula is bonded to Rf, the right end of the formula is bonded to S 1 or S 2 , The lower end of is bonded to Y.) It may be a group represented by
  • Y represents the following formula: —OCONH— (CH 2 ) r — (In the formula, r is an integer of 1 to 10, and the left end of the formula is bonded to X, and the right end of the formula is bonded to Z.) It may be a group represented by
  • a surface treatment agent comprising the fluoropolyether group-containing silicone compound.
  • the surface treatment agent of the present invention contains at least one of the fluoropolyether group-containing silicone compound represented by the general formula (Ia) and the fluoropolyether group-containing silicone compound represented by the general formula (Ib), Both of them may be included.
  • the surface treating agent of the present invention is at least one of the fluoropolyether group-containing silicone compound represented by the general formula (IIa) and the fluoropolyether group-containing silicone compound having a structure represented by the general formula (IIb). One may be included and both of these may be included.
  • the surface treatment composition of the present invention may contain any of the fluoropolyether group-containing silicone compounds having the structure represented by the general formulas (Ia), (Ib), (IIa) and (IIb). What is necessary is just to include these 2 types or more in arbitrary combinations.
  • 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.
  • 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 (Ia), (Ib), (IIa) and (IIb) In the case of general formula (IIb), it has a structure represented by general formula (IIb), and the same applies to the following).
  • 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 —).
  • 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 9) j -R 10 -R 11 - It is preferable that it is group represented by these.
  • R 9 is a perfluoroalkyl group having 1 to 15 carbon atoms (for example, linear or branched), preferably a perfluoroalkyl group having 1 to 2 carbon atoms (—CF 2 —, — C 2 F 4- ).
  • j may be 0 or 1.
  • R 10 represents the following formula: -(OC 4 F 8 ) v- (OC 3 F 6 ) a- (OC 2 F 4 ) b- (OCF 2 ) c- The perfluoropolyether group represented by these.
  • a, b, c and v each represent the number of four 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 And the sum of a, b, c and v is at least 1, preferably 1 or more and 100 or less.
  • the order of presence of each repeating unit with parentheses a, b, c, or v is described in a specific order in the formula, but the order of bonding 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 — (OCF 2 CF 2 CF 2 CF 2 ) —.
  • -(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 11 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 0 or more and 50 or less, preferably an integer of 0 to 20, for example, an integer of 1 to 20, and the sum of d and e is at least 1, preferably 1 to 10 It is.
  • 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 —
  • the perfluoropolyether group represented by these may be sufficient.
  • a ′ is an integer of 1 to 200, preferably 1 to 100.
  • 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.
  • S 2 in S 1 and the general formula (IIa) and (IIb) in the general formula (Ia) and (Ib) are both a linear organopolysiloxane group, terminal (linear group And more specifically, S 1 is one end and S 2 is both ends), and is preferably a group that binds to X described later.
  • 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).
  • S 1 may be an organopolysiloxane group represented by the following formula:
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 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 8 include unsubstituted alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and dodecyl groups; substituted alkyl groups such as chloromethyl group; phenyl groups and naphthyl groups Unsubstituted aryl group; substituted aryl groups such as 4-chlorophenyl group and 2-methylphenyl group are included.
  • n is 1 or more and 200 or less, preferably 1 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 (Ia), a plurality of compounds represented by the above general formula (Ib) A mixture of a plurality of compounds represented by the above general formula (IIa), or a mixture of a plurality of compounds represented by the above general formula (IIb), where n is the average of such mixtures It can be a real number representing the composition.
  • S 2 may be an organopolysiloxane group represented by the following formula.
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 , and n the same explanation as above applies to R 2 , R 3 , R 4 , R 5 , R 6 and R 7 , and n.
  • X is a bond between Rf and S 1 or S 2 (more specifically, Si forming a siloxane skeleton) and Y described later.
  • a linking group. X should just be a trivalent organic group.
  • X is one of the following formulas: A group represented by (wherein, the left end of the formula is bonded to Rf, the right end of the formula is bound to S 1 or S 2, the lower end of the expression is assumed to bind to Y) may be.
  • p is an integer of 1 to 10, preferably 1 to 5
  • R 13 is a divalent organic group.
  • R 13 is not particularly limited, and may be, for example, — (CH 2 ) q ′ —O— (CH 2 ) q —, where q is an integer of 1 to 20, preferably 1 to 10.
  • 'Is an integer from 1 to 10, preferably from 1 to 5, typically 1.
  • X is not limited to the above example, and any suitable divalent organic compound can be used as long as it bonds between Rf and S 1 or S 2 (more specifically, Si forming a siloxane skeleton) and Y described later. Groups can be applied.
  • Z is a silyl group containing a hydrolyzable moiety. More specifically, Z is the following formula: -SiT x R 12 3-x The silyl group represented by these may be sufficient. In this formula, T and R 12 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 12 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms (eg linear or branched), preferably an alkyl group having 1 to 22 carbon atoms, more preferably a straight 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 X and Z.
  • Y may be a divalent organic group.
  • Y represents the following formula: —OCONH— (CH 2 ) r — (Wherein, the left end of the formula is bonded to X and the right end of the formula is bonded to Z).
  • r is an integer of 1 to 10, preferably 1 to 5.
  • Y is not limited to the above example, and any appropriate divalent organic group can be applied as long as it binds between X and Z.
  • 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 having the structure represented by the general formula (IIb), in which case m is It can be a real number representing the average composition of such a mixture.
  • the fluoropolyether group-containing silicone compound represented by the general formulas (Ia), (Ib), (IIa) and (IIb) of the present invention has been described above.
  • the fluoropolyether group-containing silicone compound represented by the general formula (Ia) preferably has an average molecular weight of, for example, 1000 to 30000.
  • the fluoropolyether group-containing silicone compound represented by the general formula (Ib) preferably has an average molecular weight of, for example, 2000 to 15000.
  • the fluoropolyether group-containing silicone compound represented by the general formula (IIa) preferably has an average molecular weight of, for example, 1000 to 30000.
  • the fluoropolyether group-containing silicone compound represented by the general formula (IIb) 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 above general formula (Ia) is a silicone-based raw material represented by the following general formula (i): (Wherein R 13 and S 1 are as described above.)
  • a fluoropolyether-based material As a fluoropolyether-based material, the following general formula (ii) or (iii): R 1 —Rf— (CH 2 ) p —OH (ii) R 1 —Rf— (CH 2 ) p —NH 2 (iii) (Wherein R 1 , Rf, and p are as described above.)
  • the fluoropolyether group-containing silicone compound represented by the general formula (Ib) is represented by the following general formula (i): (Wherein R 13 and S 1 are as described above), the following general formula (ii ′) or (iii ′) as a fluoropolyether-based raw material: HO— (CH 2 ) p —Rf— (CH 2 ) p —OH (ii ′) H 2 N— (CH 2 ) p —Rf— (CH 2 ) p —NH 2 ...
  • the fluoropolyether group-containing silicone compound represented by the general formula (IIa) is a silicone-based raw material represented by the following general formula (i ′): (Wherein R 13 and S 1 are as described above), the following general formula (ii) or (iii): R 1 —Rf— (CH 2 ) p —OH (ii) R 1 —Rf— (CH 2 ) p —NH 2 (iii) (Wherein R 1 , Rf, and p are as described above.) And the following general formula (iv) as a silyl group-containing raw material: OCN- (CH 2 ) r -Z (iv) (In the formula, Z and r are as described above.) It can obtain by attaching
  • a fluoropolyether group-containing silicone compound having a structure represented by the above general formula (IIb) is used as a silicone-based raw material in the following general formula (i ′): (Wherein R 13 and S 1 are as described above.)
  • a fluoropolyether-based material the following general formula (ii ′) or (iii ′): HO— (CH 2 ) p —Rf— (CH 2 ) p —OH (ii ′) H 2 N— (CH 2 ) p —Rf— (CH 2 ) p —NH 2 ...
  • X is one of the following formulas depending on the fluoropolyether-based raw material used: (Wherein, p and R 13 are as described above, the left end of the formula is bonded to Rf, the right end of the formula is bound to S 1, the lower end of the expression is assumed to bind to Y.)
  • Y is a group represented by the following formula: —OCONH— (CH 2 ) r — (In the formula, r is as described above, and the left end of the formula is bonded to X and the right end of the formula is bonded to Z) It becomes the group represented by.
  • a fluoropolyether-based raw material a raw material in which a compound represented by the general formula (ii) and a compound represented by the general formula (ii ′) are mixed, or represented by the general formula (iii)
  • a raw material in which the compound and the compound represented by the general formula (iii ') are mixed in these raw materials, a fluorine-containing oil represented by the general formula R 1 -Rf-F described later may further be mixed)
  • a raw material in which a compound represented by the general formula (i) and a compound represented by the general formula (i ′) are mixed may be used as the silicone-based raw material.
  • the fluoropolyether group-containing silicone compound represented by the general formulas (Ia), (Ib), (IIa) and (IIb) is appropriately mixed depending on the raw materials used. Will be.
  • the above epoxy ring-opening reaction and urethane bond forming reaction may be allowed to proceed in the absence of a 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 epoxy ring-opening reaction can be carried out in the presence of a catalyst such as an acid, for example, at 0 to 150 ° C., conveniently under normal pressure.
  • the urethane bond forming reaction can be carried out in the presence of a catalyst such as organotin, organotitanium and amine compound, for example, at 20 to 150 ° C., conveniently under normal pressure.
  • a catalyst such as organotin, organotitanium and amine compound, for example, at 20 to 150 ° C., conveniently under normal pressure.
  • fluoropolyether group-containing silicone compounds of the present invention have been described with reference to production examples, the fluoropolyether group-containing silicone compound of the present invention is limited to those produced by these examples. It is not a thing.
  • 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. Specifically, at least one of the fluoropolyether group-containing silicone compound represented by the general formula (Ia) and the fluoropolyether group-containing silicone compound represented by the general formula (Ib) is included, and both of these are included. May be included. When these are used in combination, the compound represented by the general formula (Ia) and the compound represented by the general formula (Ib) may exist in a mass ratio of 1: 1 to 9: 1, for example. It is not limited to.
  • the fluoropolyether group-containing silicone compound represented by the general formula (IIa) and the fluoropolyether group-containing silicone compound represented by the general formula (IIb) is included, and both of these are included. Also good.
  • the compound represented by the general formula (IIa) and the compound represented by the general formula (IIb) may exist in a mass ratio of 1: 1 to 9: 1, for example. It is not limited to.
  • the surface treatment composition of the present invention only needs to contain any of the fluoropolyether group-containing silicone compounds represented by the general formulas (Ia), (Ib), (IIa) and (IIb), Two or more of these may be included in any combination.
  • 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 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 0 to 40 parts by mass 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 based on 100 parts by mass of the fluoropolyether group-containing silicone compounds represented by the general formulas (Ia), (Ib), (IIa) and (IIb), For example, 0 to 80 parts by mass, preferably 0 to 40 parts by mass can be contained.
  • 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 may preferably be substituted with one or more fluorine atoms.
  • the alkyl group optionally substituted by one or more fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF 2 H— and all other carbon atoms are fully substituted by fluorine.
  • a perfluoroalkyl group more preferably a perfluoroalkyl group.
  • 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 substituted with one or more fluorine atoms.
  • an alkyl group having 1 to 3 carbon atoms is an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group optionally substituted by one or more fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF 2 H— and all other carbon atoms are fully substituted by fluorine.
  • a perfluoroalkyl group more preferably a perfluoroalkyl group.
  • a ′′, b ′′, c ′′ and v ′′ each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, each independently an integer of 0 to 300, It is an integer of 1 to 300, and the sum of a ′′, b ′′, c ′′ and v ′′ is at least 1, preferably 1 to 100.
  • each repeating unit with the subscripts a ′′, b ′′, c ′′ or 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; in formula (IVa), a ′ ′′ is an integer of 1 to 100; in formula (IVb), v ′ ′′ and a ′′. 'Is 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 (Ia), (Ib), (IIa) and (IIb).
  • the fluorine-containing oil preferably has an average molecular weight of 1000 to 30000, more preferably 3000 to 30000. Thereby, 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 is based on 100 parts by mass of the fluoropolyether group-containing silicone compounds represented by the general formulas (Ia), (Ib), (IIa) and (IIb).
  • the contained silane compound can be contained, for example, in an amount of 0 to 80 parts by mass, preferably 0 to 40 parts by mass.
  • 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, preferably substituted with one or more fluorine atoms. Or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group optionally substituted by one or more fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF 2 H— and all other carbon atoms are fully substituted by fluorine.
  • a perfluoroalkyl group more preferably a perfluoroalkyl group.
  • a, b, c and v each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, each independently an integer of 0 to 200, For example, it is an integer of 1 or more and 200 or less, and the sum of a, b, c and v is at least 1, preferably 1 to 100.
  • the order of presence of each repeating unit with subscripts a, b, c or 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 ) —.
  • 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.
  • 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. In the formula, there are a plurality of X ′, Y ′, Z ′, T, R 32 , k, f, g, and x, but they may be the same or different.
  • R 31 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, preferably substituted with one or more fluorine atoms. Or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group optionally substituted by one or more fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF 2 H— and all other carbon atoms are fully substituted by fluorine.
  • a perfluoroalkyl group more preferably a perfluoroalkyl group.
  • a, b, c and v each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 200, for example, an integer of 1 to 200 Where 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 or 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, but 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.
  • 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 may contain both a non-reactive compound (for example, silicone oil and / or fluorine-containing oil) and a perfluoropolyether group-containing silane compound.
  • the substrate is based on 100 parts by mass of the fluoropolyether group-containing silicone compounds represented by the general formulas (Ia), (Ib), (IIa) and (IIb).
  • the non-reactive compound may be contained in, for example, 0 to 80 parts by weight, preferably 0 to 40 parts by weight
  • the perfluoropolyether group-containing silane compound is, for example, 0 to 80 parts by weight, preferably 0. It can be included at ⁇ 40 parts by weight.
  • the article of the present invention comprises a substrate and a fluoropolyether group-containing silicone compound or surface represented by the above-mentioned general formula (Ia), (Ib), (IIa) and / or (IIb) on the surface of the substrate And a layer (surface treatment layer) formed from a treatment agent (hereinafter simply referred to as a surface treatment composition).
  • a fluoropolyether group-containing silicone compound or surface represented by the above-mentioned general formula (Ia), (Ib), (IIa) and / or (IIb) on the surface of the substrate
  • a layer (surface treatment layer) formed from a treatment agent hereinafter simply referred to as a surface treatment composition
  • 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
  • solvents can be used alone or as a mixture of two or more.
  • hydrofluoroether is preferable, and perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) and / or 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.
  • moisture supply is not necessarily required. .
  • 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.
  • a fluoropolyether group-containing silicone compound represented by the general formula (Ia), (Ib), (IIa) and / or (IIb) in the surface treatment agent (and present) In this case, it is considered that water acts on the hydrolyzable group bonded to Si of the perfluoropolyether group-containing silane compound), and the compound can be hydrolyzed quickly.
  • 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 group bonded to Si after hydrolysis in the compounds represented by any one of the above general formulas (Ia), (Ib), (IIa) and (IIb)
  • T is a hydroxyl group
  • it is the hydroxyl group (the same applies to the following), and each other rapidly undergoes dehydration condensation.
  • silicone oil and / or fluorine-containing oil is mixed between the compounds bonded in this way.
  • the general formulas (Ia), (Ib), (IIa) And / or a bond is formed between the fluoropolyether group-containing silicone compound represented by (IIb) (and the perfluoropolyether group-containing silane compound, if present), and A bond is formed (and, if present, the silicone oil and / or fluorine-containing oil is represented by any of the general formulas (Ia), (Ib), (IIa) and / or (IIb)) Retained or captured by affinity for fluoropolyether group-containing silicone compounds (and perfluoropolyether group-containing silane compounds) That).
  • 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.
  • 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 2 As Examples 1 to 3, a mixture of fluoropolyether group-containing silicone compounds was synthesized in the following Synthesis Examples 1 to 3, respectively, and a surface treatment agent was prepared using each mixture obtained from these. A treatment layer was formed.
  • Each surface treatment agent prepared above was vacuum-deposited on "gorilla” glass (Corning).
  • the treatment conditions for vacuum deposition were set to a pressure of 3.0 ⁇ 10 ⁇ 3 Pa, and 1 mg of each surface treatment agent was deposited per one “gorilla” glass (manufactured by Corning). Thereafter, “Gorilla” glass with a deposited film (manufactured by Corning) was allowed to stand for 24 hours in an atmosphere at 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 (The symbol Me represents a methyl group.)
  • 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 by one wiping operation.
  • D Ink by one wiping operation. Can not wipe off at all
  • Example 1 and 2 using the fluoropolyether group-containing silicone compound of the present invention the water and oil repellency is higher than that in Comparative Example 3 using the composition 1 in which the control compounds 1 and 2 are simply mixed (contact angle). 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.

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Abstract

La présente invention concerne un composé inédit de type silicone contenant un groupe fluoropolyéther de structure telle que représentée par l'une des formules générales (Ia), (Ib), (IIa) et (IIb), se révélant capable de former une couche hydrofuge, oléofuge et antisalissures caractérisée par une surface très lisse. Dans ces formules, R1 représente un groupe méthyle substitué ou non substitué ; Rf représente un groupe contenant un groupe fluoropolyéther ; X représente un groupe organique trivalent ; Y représente un groupe organique divalent ; Z représente un groupe silyle contenant un site hydrolysable ; S1 représente un groupe organopolysiloxane monovalent ; S2 représente un groupe organopolysiloxane divalent ; et m est égal à 1 à 5, bornes incluses.
PCT/JP2013/062271 2012-05-18 2013-04-25 Composé de type silicone contenant un groupe fluoropolyéther WO2013172177A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106232675A (zh) * 2014-04-30 2016-12-14 大金工业株式会社 含全氟(聚)醚基的硅烷化合物
WO2017012714A1 (fr) * 2015-07-20 2017-01-26 Momentive Performance Materials Gmbh Dérivés de polyorganosiloxane substitués de manière asymétrique
WO2018041561A1 (fr) 2016-08-31 2018-03-08 Solvay Specialty Polymers Italy S.P.A. Polyamides comprenant des motifs de (per)fluoropolyéther et de poly(organosiloxane)
US20180155503A1 (en) * 2015-05-26 2018-06-07 Rudolf Gmbh Polyurethane-organopolysiloxanes
WO2021131960A1 (fr) * 2019-12-26 2021-07-01 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 et procédé de fabrication d'article

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CN106232675A (zh) * 2014-04-30 2016-12-14 大金工业株式会社 含全氟(聚)醚基的硅烷化合物
CN106232675B (zh) * 2014-04-30 2019-05-14 大金工业株式会社 含全氟(聚)醚基的硅烷化合物
US20180155503A1 (en) * 2015-05-26 2018-06-07 Rudolf Gmbh Polyurethane-organopolysiloxanes
US10626223B2 (en) * 2015-05-26 2020-04-21 Rudolf Gmbh Polyurethane-organopolysiloxanes
WO2017012714A1 (fr) * 2015-07-20 2017-01-26 Momentive Performance Materials Gmbh Dérivés de polyorganosiloxane substitués de manière asymétrique
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WO2021131960A1 (fr) * 2019-12-26 2021-07-01 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 et procédé de fabrication d'article
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