WO2017188331A1 - Composition - Google Patents

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Publication number
WO2017188331A1
WO2017188331A1 PCT/JP2017/016588 JP2017016588W WO2017188331A1 WO 2017188331 A1 WO2017188331 A1 WO 2017188331A1 JP 2017016588 W JP2017016588 W JP 2017016588W WO 2017188331 A1 WO2017188331 A1 WO 2017188331A1
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WIPO (PCT)
Prior art keywords
group
compound
formula
fluorine
organosilicon compound
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PCT/JP2017/016588
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English (en)
Japanese (ja)
Inventor
彩香 櫻井
花岡　秀典
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to CN201780025504.0A priority Critical patent/CN109071819B/zh
Priority to KR1020187034260A priority patent/KR102370256B1/ko
Publication of WO2017188331A1 publication Critical patent/WO2017188331A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a composition for forming a film capable of imparting water repellency and oil repellency to various substrates.
  • Patent Document 1 as a treating agent that can be applied to a glass substrate having a bent shape to produce a water-slidable glass article, it contains linear polydimethylsiloxane and fluoroalkylsilane, and further includes a solvent and a catalyst.
  • a composition comprising
  • the inventors of the present invention have found that the film described in Patent Document 1 may not have sufficient oil repellency, adhesion and film-forming properties.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition capable of improving the film forming property while achieving both the water repellency and the oil repellency of the film.
  • the present inventors have achieved both the water repellency and oil repellency of the resulting film when using a composition containing a predetermined organosilicon compound, metal alkoxide, and fluorine-containing organosilicon compound.
  • the present invention has been completed by finding that the film-forming property can be improved.
  • the present invention includes the following inventions.
  • a coating composition comprising a fluorine-containing organosilicon compound (f) having a functional group bonded to a silicon atom.
  • the compound (a) is a compound represented by the formula (I).
  • R a represents a trialkylsilyl group-containing molecular chain
  • a a1 independently represents a hydrolyzable group.
  • Z a1 represents a trialkylsilyl group-containing molecular chain, a hydrocarbon chain-containing group, a siloxane skeleton-containing group, or a hydrolyzable group.
  • M represents a trivalent or tetravalent metal atom capable of forming a metal alkoxide.
  • a b1 independently represents an alkoxy group having 1 to 4 carbon atoms.
  • k represents an integer of 3 or 4 depending on M.
  • a f2 independently represents a hydrolyzable group, a fluorine-containing alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
  • the content ratio of the fluorine-containing organosilicon compound (f) and the organosilicon compound (a) (fluorine-containing organosilicon compound (f) / organosilicon compound (a)) is 7 /
  • the coating composition according to any one of [1] to [4], which is 1 or more and 20/1 or less.
  • the content ratio of the metal alkoxide (b) to the fluorine-containing organosilicon compound (f) is 0.01 or more in molar ratio.
  • composition of the present invention contains a predetermined organosilicon compound, metal alkoxide, and fluorine-containing organosilicon compound, it is possible to achieve both the water repellency, oil repellency and adhesion of the resulting film, and also film forming properties. It becomes good.
  • composition is an organic compound in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom.
  • the metal alkoxide (b) itself contributes less to water repellency and oil repellency than the organosilicon compound or the fluorine-containing organosilicon compound (f), the metal alkoxide (b) It is considered that the water- and oil-repellent properties of the trialkylsilyl group-containing molecular chain and the fluorine-containing group are emphasized, and the homogeneity of the resulting film is also improved.
  • the organosilicon compound (a) includes, in one molecule, at least one trialkylsilyl group-containing molecular chain bonded to the central silicon atom, and at least one hydrolyzable group bonded to the central silicon atom.
  • the organosilicon compound (a) is preferably a compound represented by the following formula (I).
  • R a represents a trialkylsilyl group-containing molecular chain
  • a a1 independently represents a hydrolyzable group
  • Z a1 represents a trialkylsilyl group-containing molecular chain, a hydrocarbon chain-containing group, a siloxane skeleton-containing group, or a hydrolyzable group.
  • the trialkylsilyl group-containing molecular chain is a monovalent group having a structure in which the trialkylsilyl-containing group is bonded to the end of the molecular chain, and the trialkylsilyl-containing group is bonded to the molecular chain.
  • the water repellency and oil repellency of the film formed from the composition of the invention are improved.
  • the presence of the trialkylsilyl group-containing molecular chain reduces the friction between the droplet (water droplet, oil droplet, etc.) and the coating, and facilitates the movement of the droplet.
  • chemical durability and / or physical durability are improved, and heat resistance and light resistance are improved. Even in the case where the alkyl group of the trialkylsilyl-containing group is replaced with a fluoroalkyl group, the water repellency and oil repellency at the film interface (surface) can be similarly improved.
  • the trialkylsilyl-containing group is a group containing at least one trialkylsilyl group, preferably two or more, more preferably three trialkylsilyl groups.
  • the trialkylsilyl-containing group is preferably a group represented by the formula (s1).
  • R s1 represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or the trialkylsilyloxy group may be substituted with a fluorine atom. However, when all R s1 is a hydrocarbon group, R s1 is an alkyl group. * Represents a bond. ]
  • the hydrocarbon group represented by R s1 preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and still more preferably 1 to 2.
  • the total carbon number of the three R s1 is preferably 9 or less, more preferably 6 or less, and even more preferably 4 or less.
  • the hydrocarbon group represented by R s1 is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • a plurality of R s1 may be the same or different and are preferably the same. Is preferably at least one of methyl group of the three R s1, more preferably at least two of a methyl group, and particularly preferably all three R s1 is a methyl group.
  • the hydrogen atom contained in the trialkylsilyl group and trialkylsilyloxy group represented by R s1 may be substituted with a fluorine atom.
  • the number of fluorine atoms substituted is preferably 1 or more, more preferably 3 or more, and preferably 2 ⁇ A + 1 or less, where A is the number of carbon atoms.
  • the hydrogen atom contained in the alkyl group is substituted with a fluorine atom
  • the number of substituted alkyl groups can be appropriately selected within a range of 1 to 3 per silicon atom.
  • At least one of R s1 may be a trialkylsilyloxy group.
  • the trialkylsilyloxy group include a group in which an oxygen atom is bonded to a silicon atom of a group (trialkylsilyl group) in which R s1 is a hydrocarbon group (alkyl group).
  • R s1 is a trialkylsilyloxy group
  • examples of the group in which at least one of R s1 is a trialkylsilyloxy group include groups represented by the following formulae.
  • the trialkylsilyl group may be bonded to the end (free end side) of the molecular chain, particularly to the end (free end side) of the main chain (longest straight chain) of the molecular chain. preferable.
  • the molecular chain to which the trialkylsilyl group is bonded is preferably linear or branched, and is preferably linear.
  • the molecular chain preferably includes a dialkylsiloxane chain, and preferably includes a linear dialkylsiloxane chain.
  • the molecular chain may contain a divalent hydrocarbon group. Even if a part of the molecular chain is a divalent hydrocarbon group, since the remainder is a dialkylsiloxane chain, the chemical durability and / or physical durability of the resulting film is good.
  • the molecular chain is preferably a group represented by the formula (s2).
  • R s2 represents an alkyl group having 1 to 4 carbon atoms.
  • Z s1 represents —O— or a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
  • Y s1 represents a single bond or —Si (R s2 ) 2 —L s1 —.
  • L s1 represents a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
  • * On the left side represents a bond with a central silicon atom, and * on the right side represents a bond with a trialkylsilyl-containing group.
  • the number of carbon atoms of the alkyl group represented by R s2 is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
  • Examples of the alkyl group represented by R s2 include a methyl group, an ethyl group, a propyl group, and a butyl group. A methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
  • N1 is preferably 1 to 100, more preferably 1 to 80, still more preferably 1 to 50, and particularly preferably 1 to 30.
  • the number of carbon atoms of the divalent hydrocarbon group represented by Z s1 or L s1 is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4.
  • the divalent hydrocarbon group is preferably chain-like, and when it is chain-like, it may be either linear or branched.
  • the divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and preferably an alkanediyl group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.
  • a part of —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
  • two consecutive —CH 2 — are not simultaneously replaced with —O—, and —CH 2 — adjacent to the Si atom is not replaced with —O—.
  • the number of carbon atoms between —O— and —O— is preferably 2 to 4, and more preferably 2 to 3 preferable.
  • Specific examples of the group in which a part of the divalent hydrocarbon group is replaced by —O— include a group having a (poly) ethylene glycol unit, a group having a (poly) propylene glycol unit, and the like. it can.
  • Z s1 is —O— and Y s1 is a single bond, that is, the molecular chain is composed only of repeating dialkylsilyloxy groups.
  • the dialkylsiloxane chain consists only of repeating dialkylsilyloxy groups, the resulting film has good chemical durability and / or physical durability.
  • Examples of the molecular chain contained in the trialkylsilyl group-containing molecular chain include a molecular chain represented by the following formula.
  • p1 represents an integer of 1 to 30, and * represents a bond bonded to a silicon atom or a trialkylsilyl group forming a polysiloxane skeleton.
  • the total number of atoms constituting the trialkylsilyl group-containing molecular chain is preferably 24 or more, more preferably 40 or more, still more preferably 50 or more, and preferably 1200 or less. Is 700 or less, more preferably 250 or less.
  • the trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s1).
  • the trialkylsilyl group-containing molecular chain is more preferably a group represented by the following formula (s1-1), and even more preferably a group represented by the following formula (s1-1-1).
  • R s2 , Y s1 , Z s1 , and n1 are as defined above.
  • R s3 represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond with a silicon atom.
  • trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s1-2), more preferably a group represented by the following formula (s1-2-1).
  • R s2 , R s3 , Y s1 , Z s1 , and n1 are as defined above. * Represents a bond with a silicon atom.
  • Examples of the alkyl group represented by R s3 include the same groups as the alkyl groups exemplified as the hydrocarbon group represented by R s1 , and the alkyl group preferably has 1 to 3 carbon atoms. Preferably it is 1-2. Further, the total carbon number of R s3 contained in * -Si (R s3 ) 3 is preferably 9 or less, more preferably 6 or less, and still more preferably 4 or less. Further, among R s3 contained in * -Si (R s3 ) 3 , at least one is preferably a methyl group, two or more R s3 are preferably methyl groups, and all three R s3 are all A methyl group is particularly preferred.
  • Examples of the trialkylsilyl group-containing molecular chain include a group represented by the formula (s1-I).
  • the following formulas (s1-I-1) to (s1-I-50) are specific examples of the group represented by the formula (s1-I), but are not limited thereto.
  • a plurality of R s20 and a plurality of R s10 contained therein may be the same or different.
  • the number of trialkylsilyl group-containing molecular chains bonded to the central silicon atom is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.
  • the hydrolyzable group When the hydrolyzable group is bonded to a silicon atom, the hydrolyzable group may be a group that gives a hydroxy group (silanol group) by hydrolysis.
  • the number of carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group Preferred examples include 1-4 alkoxy groups; acetoxy groups; chlorine atoms; isocyanate groups; Among these, an alkoxy group having 1 to 4 carbon atoms is preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.
  • the number of hydrolyzable groups bonded to the central silicon atom is 1 to 3, and preferably 2 to 3.
  • a group in which a hydrolyzable group is bonded to a silicon atom may be referred to as a hydrolyzable silicon group.
  • the siloxane skeleton-containing group is a monovalent group containing a siloxane unit (Si—O—), and may be composed of a smaller number of atoms than the number of atoms constituting the trialkylsilyl group-containing molecular chain. That's fine.
  • the siloxane skeleton-containing group is a group having a shorter length than the trialkylsilyl group-containing molecular chain or a small steric spread (bulk height).
  • the siloxane skeleton-containing group may contain a divalent hydrocarbon group.
  • the siloxane skeleton-containing group is preferably a group represented by the following formula (s2).
  • R s2 has the same meaning as described above.
  • R s5 represents a hydrocarbon group or a hydroxy group, —CH 2 — contained in the hydrocarbon group may be replaced by —O—, and the hydrogen atom contained in the hydrocarbon group is a fluorine atom. May be substituted.
  • Z s2 represents —O— or a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced with —O—.
  • Y s2 represents a single bond or —Si (R s2 ) 2 —L s2 —.
  • L s2 represents a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
  • n2 represents an integer of 0 to 5. * Represents a bond with a silicon atom.
  • Examples of the hydrocarbon group represented by R s5 include the same groups as the hydrocarbon group represented by R s1 , an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable.
  • the number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
  • Examples of the divalent hydrocarbon group represented by Z s2 or L s2 include the same groups as the divalent hydrocarbon group represented by Z s1 , and the number of carbon atoms is preferably 1 to 10. More preferably, it is 1-6, and more preferably 1-4.
  • the divalent hydrocarbon group represented by Z s2 or L s2 is preferably a divalent aliphatic hydrocarbon group, and more preferably a linear or branched alkanediyl group. .
  • N2 is preferably 1 to 5, and more preferably 1 to 3.
  • siloxane skeleton-containing group examples include groups represented by the following formulas.
  • the hydrocarbon chain-containing group is a monovalent group including a hydrocarbon chain and has a hydrocarbon chain portion having a smaller number of carbon atoms than the number of atoms constituting the molecular chain of the trialkylsilyl group-containing molecular chain. Good. Moreover, it is preferable that the number of carbon atoms of the longest straight chain of the hydrocarbon chain is smaller than the number of atoms constituting the longest straight chain of the trialkylsilyl group-containing molecular chain.
  • the hydrocarbon chain-containing group may be composed only of a hydrocarbon group (hydrocarbon chain), and —CH 2 — contained in the hydrocarbon chain may be replaced by —O—, and the hydrocarbon group ( It is preferably composed of only hydrocarbon chains.
  • the carbon number of the hydrocarbon chain portion means the number of carbon atoms constituting the hydrocarbon group (hydrocarbon chain) in the oxygen non-substituted hydrocarbon chain-containing group, and includes the oxygen-substituted hydrocarbon chain. In the group, it means the number of carbon atoms counted by replacing —O— with —CH 2 —.
  • a hydrocarbon chain-containing group will be described by taking an oxygen-nonsubstituted hydrocarbon chain-containing group (that is, a monovalent hydrocarbon group) as an example. In any description, —CH 2 — It is possible to replace some of them with —O—.
  • the number of carbon atoms of the hydrocarbon chain-containing group is preferably 1 to 3, more preferably 1.
  • the hydrocarbon chain-containing group (in the case of a hydrocarbon group) may be branched or linear.
  • the hydrocarbon chain-containing group in the case of a hydrocarbon group) is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group, and more preferably a saturated aliphatic hydrocarbon chain-containing group.
  • the saturated aliphatic hydrocarbon chain-containing group is preferably an alkyl group such as a methyl group, an ethyl group, or a propyl group.
  • the organosilicon compound (a) is preferably a compound represented by the following formula (I-1), and more preferably a compound represented by the formula (I-1-1).
  • a a1 , Z a1 , Z s1 , Y s1 , R s2 , R s3 , n1 are as defined above.
  • the organosilicon compound (a) may be a compound represented by the formula (I-2), preferably a compound represented by the formula (I-2-1).
  • a a1 , Z a1 , Z s1 , Y s1 , R s2 , R s3 , and n2 are as defined above.
  • organosilicon compound (a) examples include groups represented by the formula (II).
  • the following formulas (II-1) to (II-100) are specific examples of the group represented by the formula (II), but are not limited thereto.
  • a plurality of A a10 , a plurality of R s20, and a plurality of R s10 contained therein may be the same or different.
  • Examples of the method for synthesizing the organosilicon compound (a) include the following methods.
  • a compound in which a trialkylsilyl group-containing molecular chain and a halogen atom (preferably a chlorine atom) are bonded, and a compound in which three or more (especially four) hydrolyzable groups are bonded to a silicon atom It can manufacture by making this react.
  • a compound in which halogen atoms are bonded to both ends of a dialkylsiloxane chain (hereinafter, “dihalogenated dialkylsiloxane”), a tris (trialkylsilyloxy) silyl group, an M 1 O— group ( M 1 represents an alkali metal) and can be produced by reacting a compound (hereinafter referred to as “alkali metal silyl oxide”) and a compound having four hydrolyzable groups bonded to a silicon atom.
  • reaction order of these compounds is not limited, it is preferable to first react a dihalogenated dialkylsiloxane and an alkali metal silyl oxide, and then react a compound having four hydrolyzable groups bonded to a silicon atom.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A chlorine atom is preferable.
  • the alkali metal is preferably lithium.
  • the alkali metal silyl oxide can be produced, for example, by reacting an alkyl alkali metal with a compound in which a tris (trialkylsilyloxy) silyl group and a hydroxy group are bonded.
  • the organic alkali metal compound include alkyllithiums such as n-butyllithium, sec-butyllithium and tert-butyllithium, with n-butyllithium being particularly preferred.
  • the organosilicon compound (a) is prepared by reacting, for example, alkali metal silyloxide and cyclic dimethylsiloxane, and then the silicon atom has three hydrolyzable groups and a halogen atom (particularly a chlorine atom). It can also be produced by reacting a compound in which one) is bonded.
  • the organosilicon compound (a) is reacted with alkali metal silyl oxide and cyclic dimethylsiloxane to obtain dimethylsiloxane having a hydroxyl group at the terminal, and then reacted with tetraalkoxysilane. It can also be manufactured.
  • the content of the organosilicon compound (a) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more in 100% by mass of the composition. Yes, it is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.
  • the metal alkoxide (b) is a compound in which an alkoxy group is bonded to a metal atom, and a site having a spacer function can be formed in a film formed from the composition of the present invention.
  • the water repellency and oil repellency improving action by the trialkylsilyl group-containing molecular chain and fluorine-containing group can be enhanced, and the film-forming property is also improved.
  • the metal alkoxide (b) is preferably a compound represented by the formula (II).
  • the compound represented by the formula (II) may be a hydrolysis condensate thereof.
  • the hydrolysis-condensation product means a compound in which all or a part of alkoxy groups contained in each compound (II) are condensed by hydrolysis.
  • M represents a trivalent or tetravalent metal atom capable of forming a metal alkoxide.
  • a b1 independently represents an alkoxy group having 1 to 4 carbon atoms.
  • k represents an integer of 3 or 4 depending on the valence of M.
  • M is a metal atom that can be bonded to an alkoxy group to form a metal alkoxide, and the metal atom includes a semimetal such as Si or Ge.
  • M include trivalent metals such as Al, Fe and In; tetravalent metals such as Hf, Si, Ti, Sn and Zr; and preferably trivalent metals such as Al; Si, Ti, Sn, Tetravalent metals such as Zr; more preferably Al, Si, Ti, Zr, and particularly preferably Si.
  • These metal alkoxides can be easily liquefied. Further, when M is a trivalent metal, k represents 3, and when M is a tetravalent metal, k represents 4.
  • the alkoxy group represented by A b1 is more preferably an alkoxy group having 1 to 2 carbon atoms.
  • the hydrolyzable group of the organosilicon compound (a) and the alkoxy group of the metal alkoxide (b) may be the same or different, but are preferably the same, both of which are alkoxy groups having 1 to 4 carbon atoms. It is preferable that
  • Examples of the metal alkoxide (b) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; trialkoxyaluminums such as triethoxyaluminum, tripropoxyaluminum, and tributoxyaluminum; Trialkoxy iron; trialkoxy indium such as trimethoxy indium, triethoxy indium, tripropoxy indium, tributoxy indium; tetraalkoxy hafnium such as tetramethoxy hafnium, tetraethoxy hafnium, tetrapropoxy hafnium, tetrabutoxy hafnium; tetramethoxy titanium, Tetraalkoxy such as tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc
  • Tan tetramethoxy tin, tetraethoxy tin, tetra propoxy tin, tetraalkoxy tin, such as tetrabutoxy tin; tetramethoxy zirconium, tetraethoxy zirconium, tetra propoxy zirconium, tetra-alkoxy zirconium, such as tetrabutoxyzirconium; and the like.
  • the content of the metal alkoxide (b) is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more in 100% by mass of the composition.
  • the content is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.
  • the ratio of metal alkoxide (b) to organosilicon compound (a) is preferably 1/10 or more on a molar basis, More preferably 1/1 or more, still more preferably 2/1 or more, and preferably 100/1 or less, more preferably 50/1 or less, still more preferably 30/1 or less, and even more preferably 25 / 1 or less.
  • the fluorine-containing organosilicon compound (f) has at least one fluorine-containing group bonded to the central silicon atom and at least one hydrolyzable group bonded to the central silicon atom in one molecule. .
  • the fluorine-containing group is a group including a structure in which a carbon atom and a fluorine atom are bonded, and may be a fluorinated hydrocarbon group which may have a substituent. It may be a group in which bonded silicon atoms and —O— are alternately arranged (sometimes referred to as a hydrolyzable silane oligomer residue).
  • the fluorine-containing organosilicon compound (f) is preferably a compound represented by either the following formula (III-1) or (III-2).
  • each of the compounds represented by the formula (III-1) or (III-2) may be a hydrolysis condensate (a group in which a hydrolyzable group contained in the compound is condensed by hydrolysis). Good.
  • R f1 represents a fluorocarbon-containing group having 1 to 8 carbon atoms.
  • a f1 independently represents a hydrolyzable group.
  • Z f1 represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group, or a hydrolyzable group.
  • R f2 represents a hydrolyzable silane oligomer residue.
  • a f2 independently represents a hydrolyzable group, a fluorine-containing alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
  • Examples of the hydrolyzable group represented by A f1 , A f2 and Z f1 include the same groups as the hydrolyzable groups of the organosilicon compound (a), preferably an alkoxy group or an isocyanate group, An alkoxy group having 4 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.
  • the hydrolyzable groups of the fluorine-containing organosilicon compound (f) and the organosilicon compound (a) may be the same or different and are preferably the same, both of which are alkoxy groups having 1 to 4 carbon atoms. Preferably there is.
  • the number of atoms of the siloxane skeleton-containing group represented by Z f1 , the hydrocarbon chain-containing group, and the fluorocarbon-containing group represented by R f1 is the molecular chain (preferably trialkylsilyl group and hydrolysate in the organic compound (a)).
  • the number of atoms is preferably smaller than the number of atoms of the chain or cyclic hydrocarbon and / or the chain or cyclic dialkylsiloxane connecting the decomposable silicon group.
  • the longest straight chain carbon number contained in the siloxane skeleton-containing group, hydrocarbon chain-containing group or R f1 represented by R f1 in Z f1 is greater than the number of atoms in the trialkylsilyl group-containing molecular chain. It is preferable that the amount is small.
  • the structure derived from the metal alkoxide (b) can act as a spacer.
  • Siloxane skeleton-containing group represented by Z f1 the hydrocarbon chain-containing group, a siloxane skeleton-containing group represented by Z a2, include hydrocarbon chains containing groups and each similar group.
  • the fluorocarbon-containing group represented by R f1 is a monovalent group including a structure in which a fluorine atom is bonded to a carbon atom, and is preferably a group having a fluoroalkyl group at the end, and a fluoroalkyl group (preferably trifluoro). A group having a methyl group) at the terminal is preferable.
  • a group represented by the formula (f1) is preferable.
  • R f3 represents a fluorine-containing alkyl group having 1 to 20 carbon atoms.
  • R f4 represents a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms.
  • R b4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • L represents any of —O—, —COO—, —OCO—, —NR f5 —, —NR f5 CO—, and —CONR f5 —.
  • R f5 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms.
  • h1 to h5 are integers of 0 to 100, and the total value of h1 to h5 is 100 or less. Further, the order of each repeating unit attached with h1 to h5 and enclosed in parentheses is arbitrary in the formula. * Represents a bond. ]
  • the fluorine-containing alkyl group represented by R f3 or R f4 has 1 to 20, preferably 1 to 12, more preferably 1 to 10, and more preferably 1 to 5. Further preferred.
  • the number of fluorine atoms substituted in the fluorine-containing alkyl group represented by R f3 or R f4 is 1 or more and 2A + 1 or less, where A is the number of carbon atoms contained in the fluorine-containing alkyl group, and 2A + 1 That is, the fluorine-containing alkyl group is preferably a perfluoroalkyl group.
  • Examples of the alkyl group represented by R b4 include the same groups as the alkyl groups exemplified as the hydrocarbon group represented by R s1 .
  • L f1 is preferably any one of —O—, —COO—, and —OCO—.
  • h1 is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 2.
  • h2 is preferably from 0 to 15, and more preferably from 0 to 10.
  • h3 is preferably 0 to 5, and more preferably 0 to 2.
  • h4 is preferably from 0 to 4, more preferably from 0 to 2.
  • h5 is preferably from 0 to 4, more preferably from 0 to 2.
  • the total value of h1 to h5 is preferably 3 or more, more preferably 5 or more, and preferably 80 or less, more preferably 50 or less, and still more preferably 20 or less.
  • R f3 is a perfluoroalkyl having 1 to 5 carbon atoms
  • R f4 is a fluorine atom or a perfluoroalkyl having 1 to 5 carbon atoms
  • R b4 is a hydrogen atom
  • h3, h4, and h5 are all 0. It is preferable that h1 is 1 to 5 and h2 is 0 to 5.
  • fluorocarbon-containing group examples include groups represented by the following formulas.
  • R f3 and R b4 are as defined above, R f3 is preferably a C 1-12 perfluoroalkyl group, and R b4 is preferably a hydrogen atom.
  • R2 is 5 to 20, preferably 8 to 15.
  • r3 is 1 to 7, preferably 2 to 6.
  • r4 is 1 to 10, preferably 3 to 7.
  • r5 is 1 to 6, preferably 2 to 4.
  • Examples of the group represented by the formula (f1-1) include a group represented by the following formula.
  • Examples of the group represented by the formula (f1-2) include a group represented by the following formula.
  • L f2 represents an alkanediyl group having 5 to 20 carbon atoms.
  • Examples of the group represented by the formula (f1-3) include a group represented by the following formula.
  • L f2 represents an alkanediyl group having 5 to 20 carbon atoms.
  • Examples of the group represented by the formula (f1-4) include a group represented by the following formula.
  • L f2 represents an alkanediyl group having 5 to 20 carbon atoms.
  • Examples of the group represented by the formula (f1-5) include a group represented by the following formula.
  • L f3 represents an alkanediyl group having 1 to 6 carbon atoms.
  • the fluorocarbon-containing group may be a fluoroalkylaryl group, a fluoroalkylalkenyl group, a fluoroalkylalkynyl group, or the like.
  • the fluoroalkylaryl group include (fluoro C 1-8 alkyl) phenyl group and (fluoro C 1-8 alkyl) naphthyl group.
  • the fluoroalkylalkenyl group include (fluoro C 1-17 alkyl) vinyl group.
  • Examples of the fluoroalkylalkynyl group include a ( fluoroC 1-17 alkyl) ethynyl group.
  • Z f1 is preferably a siloxane skeleton-containing group or a hydrolyzable group, and more preferably a hydrolyzable group.
  • the hydrolyzable silane oligomer residue represented by R f2 is a compound containing a silicon atom and a hydrolyzable group bonded to the silicon atom (hereinafter referred to as “hydrolyzable silane monomer”).
  • the number of silicon atoms contained in the hydrolyzable silane oligomer residue is, for example, 3 or more, preferably 5 or more, more preferably 7 or more.
  • the number of silicon atoms contained in the hydrolyzable silane oligomer residue is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.
  • hydrolyzable silane oligomer residue has an alkoxy group
  • examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group and an ethoxy group are preferable.
  • the hydrolyzable silane oligomer residue may have one or more of these alkoxy groups, and preferably has one.
  • the hydrolyzable silane oligomer residue is preferably a group represented by the formula (f2).
  • a f3 independently represents a hydrolyzable group, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms.
  • h6 is an integer of 0 or more and 100 or less. * Represents a bond with Si.
  • Examples of the hydrolyzable group represented by A f3 include an alkoxy group having 1 to 4 carbon atoms (preferably 1 to 2) such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; a hydrogen atom; a cyano group; an allyl group An alkoxy group is preferable, and an ethoxy group, a methoxy group, and an isocyanate group are more preferable.
  • h6 is preferably 0 or more and 10 or less, and more preferably 0 or more and 7 or less.
  • a f3 is preferably a hydrolyzable group or a fluorinated alkyl group having 1 to 4 carbon atoms, and at least one of A f3 is preferably a fluorinated alkyl group having 1 to 4 carbon atoms. Further, at least one of A f3 is preferably a hydrolyzable group (particularly a methoxy group or an ethoxy group).
  • hydrolyzable silane oligomer residue examples include groups represented by the following formulas.
  • Examples of the compound represented by the formula (III-1) include a compound represented by the following formula.
  • r1 is 1 to 15, preferably 1 to 12, and more preferably 1 to 6.
  • Examples of the compound represented by the formula (III-1) also include a compound represented by the following formula.
  • r2 is 5 to 20, preferably 8 to 15.
  • r3 is 1 to 7, preferably 2 to 6.
  • r4 is 1 to 10, preferably 2 to 8, and more preferably 2 to 5.
  • r5 is 1 to 5, preferably 2 to 4.
  • r6 is 2 to 10, preferably 2 to 8.
  • r7 is 2 to 10, preferably 3 to 7.
  • Examples of the compound represented by the formula (III-2) include compounds represented by the following formula.
  • the content of the fluorine-containing organosilicon compound (f) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 1% by mass or more in 100% by mass of the composition. It is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less.
  • the ratio of the fluorine-containing organosilicon compound (f) to the organosilicon compound (a) is 1 in molar ratio.
  • the content ratio of the metal alkoxide (b) and the fluorine-containing organosilicon compound (f) is 0.01 by molar ratio.
  • it is 0.1 or more, more preferably 0.2 or more, and preferably 50 or less, more preferably 10 or less, and even more preferably 5 or less.
  • the composition of the present invention preferably further contains a solvent (c).
  • Solvent (c) includes water; hydrophilic organic solvents such as alcohol solvents, ether solvents, ketone solvents, ester solvents and amide solvents; hydrophobic solvents such as aromatic hydrocarbon solvents and saturated hydrocarbon solvents These may be used alone or in combination of two or more.
  • the alcohol solvent include methanol, ethanol, propanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, and diethylene glycol.
  • the ether solvent include dimethoxyethane, tetrahydrofuran, and dioxane.
  • Examples of the solvent include acetone and methyl ethyl ketone, examples of the ester solvent include ethyl acetate and butyl acetate, examples of the amide solvent include dimethylformamide, and examples of the aromatic hydrocarbon solvent include Examples of the saturated hydrocarbon solvent include benzene, toluene, and xylene. Examples of the saturated hydrocarbon solvent include hexane and cyclohexane.
  • alcohol solvents and ketone solvents are preferable and may contain water. When water is contained, the content of water in the solvent (c) is preferably 0.1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 90% by mass or less. More preferably, it is 70 mass% or less, More preferably, it is 50 mass% or less.
  • the solvent (c) is preferably 0.1 parts by mass or more, more preferably with respect to 1 part by mass in total of the organosilicon compound (a), the metal alkoxide (b) and the fluorinated organosilicon compound (f). Is 5 parts by mass or more, more preferably 10 parts by mass or more, particularly preferably 12 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 50 parts by mass or less. is there. When the amount of the solvent (c) is within this range, the thickness of the film can be easily controlled.
  • the composition of the present invention may further contain a catalyst (d).
  • the catalyst (d) is not particularly limited as long as it can act as a hydrolysis catalyst for a hydrolyzable group bonded to a silicon atom, and examples thereof include acidic compounds; basic compounds; organometallic compounds; Examples of the acidic compound include inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid; Examples of the basic compound include ammonia, amines, and the like.
  • organometallic compound examples include organometallic compounds having a metal element such as Al, Fe, Zn, and Sn as a central metal, and organoaluminum compounds such as aluminum acetylacetone complex and aluminum ethylacetoacetate complex; Organic iron compounds; organic zinc compounds such as zinc acetylacetonate monohydrate, zinc naphthenate, and zinc octylate; organic tin compounds such as dibutyltin diacetate complex; Especially, as a catalyst (d), an organometallic compound and an acidic compound are preferable, and an organoaluminum compound and hydrochloric acid are more preferable.
  • organometallic compounds having a metal element such as Al, Fe, Zn, and Sn as a central metal
  • organoaluminum compounds such as aluminum acetylacetone complex and aluminum ethylacetoacetate complex
  • Organic iron compounds organic zinc compounds such as zinc acetylacetonate monohydrate, zinc naphthenate, and
  • the catalyst (d) is preferably 0.0001 parts by mass or more, more preferably 100 parts by mass or more with respect to 100 parts by mass in total of the organosilicon compound (a), the metal alkoxide (b) and the fluorine-containing organosilicon compound (f). Is 0.0002 parts by mass or more, more preferably 0.001 parts by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less. Further, when an acidic compound is used as the catalyst, the catalyst (d) is 0.001 mass relative to 100 mass parts in total of the organosilicon compound (a), the metal alkoxide (b) and the fluorinated organosilicon compound (f).
  • the catalyst (d) is 0.0001 with respect to 100 parts by mass in total of the organosilicon compound (a), the metal alkoxide (b) and the fluorinated organosilicon compound (f). It is preferably at least part by mass, more preferably at least 0.0002 part by mass, even more preferably at least 0.001 part by mass, preferably at most 0.1 part by mass, more preferably at least 0.05 part by mass. Or less.
  • composition of the present invention is an antioxidant, a rust inhibitor, a UV absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-bioadhesive agent, a deodorant, as long as the effects of the present invention are not impaired.
  • Various additives such as pigments, flame retardants and antistatic agents may be included.
  • antioxidants examples include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, hindered amine-based antioxidants, and the like.
  • phenolic antioxidant examples include n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, 2, 2-thio-diethylene-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tri-ethylene glycol-bis- [3- (3-t-butyl-5-methyl -4-hydroxyphenyl) propionate], 3,9-bis [2- ⁇ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ -1,1-dimethylethyl] -2, 4,8,10-tetraoxaspiro [5.5] undecane, tetrakis ⁇ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid ⁇ pentaeryth Cyl ester, 2-t-butyl-6-
  • sulfur-based antioxidant examples include 3,3′-thiodipropionic acid di-n-dodecyl ester, 3,3′-thiodipropionic acid di-n-tetradecyl ester, and 3,3′-thiodipropion ester.
  • examples include acid di-n-octadecyl ester, tetrakis (3-dodecylthiopropionic acid) pentaerythritol ester, and the like.
  • Examples of the phosphorus antioxidant include tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6- Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4 Examples include '-biphenylene diphosphonite, bis- [2,4-di-t-butyl, (6-methyl) phenyl] ethyl phosphite, and the like.
  • hindered amine antioxidant examples include sebacic acid bis (2,2,6,6-tetramethyl-4-piperidyl) ester (melting point: 81 to 86 ° C.), 2,2,6,6-tetramethyl-4- Piperidyl methacrylate (melting point: 58 ° C.), poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6, 6-tetramethyl-4-piperidyl) imino ⁇ -1,6-hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ] and the like.
  • the rust inhibitor examples include alkanolamines such as triethanolamine; quaternary ammonium salts; alkanethiols; imidazoles such as imidazoline, imidazole, alkylimidazoline derivatives, benzimidazole, 2-mercaptobenzimidazole, and benzotriazole; metavanadic acid Sodium; bismuth citrate; phenol derivatives; aliphatic amines such as alkylamines and polyalkenylamines, aromatic amines, ethoxylated amines, cyanoalkylamines, cyclohexylamine benzoate, aliphatic diamines such as alkylenediamine, aromatic diamines, etc.
  • alkanolamines such as triethanolamine
  • quaternary ammonium salts such as imidazoline, imidazole, alkylimidazoline derivatives, benzimidazole, 2-mercaptobenzimidazole, and benzotri
  • Examples of the ultraviolet absorber / light stabilizer include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl].
  • Examples of the fungicide / antibacterial agent include 2- (4-thiazolyl) benzimidazole, sorbic acid, 1,2-benzisothiazolin-3-one, (2-pyridylthio-1-oxide) sodium, dehydroacetic acid, 2-methyl -5-chloro-4-isothiazolone complex, 2,4,5,6-tetrachlorophthalonitrile, methyl 2-benzimidazole carbamate, methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate, mono or dibromocyano
  • Examples include acetamides, 1,2-dibromo-2,4-dicyanobutane, 1,1-dibromo-1-nitropropanol and 1,1-dibromo-1-nitro-2-acetoxypropane.
  • biological adhesion inhibitor examples include tetramethylthiuram disulfide, bis (N, N-dimethyldithiocarbamate) zinc, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, dichloro-N-((dimethylamino ) Sulfonyl) fluoro-N- (P-tolyl) methanesulfenamide, pyridine-triphenylborane, N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide, cuprous thiocyanate ( 1), cuprous oxide, tetrabutylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zinc ethylenebisdithiocarbamate, 2,3,5,6-tetrachloro-4- (methyl) Sulfonyl) pyridine, N- (2,4,6-trichloroph
  • deodorizer examples include lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediaminepolyacetic acid, alkane-1,2-dicarboxylic acid, alkene-1,2-dicarboxylic acid, cycloalkane-1 , 2-dicarboxylic acid, cycloalkene-1,2-dicarboxylic acid, organic acids such as naphthalenesulfonic acid; fatty acid metals such as zinc undecylenate, zinc 2-ethylhexanoate, zinc ricinoleate; iron oxide, iron sulfate, Zinc oxide, zinc sulfate, zinc chloride, silver oxide, copper oxide, metal (iron, copper, etc.) chlorophyllin sodium, metal (iron, copper, cobalt etc.) phthalocyanine, metal (iron, copper, cobalt etc.) tetrasulfonic acid phthalocyanine, Metal compounds such as titanium dioxide, visible light responsive
  • the pigment examples include carbon black, titanium oxide, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, perylene or perine pigment, quinophthalone pigment, diketopyrrolo-pyrrole pigment, dioxazine pigment, disazo condensation pigment, Examples include benzimidazolone pigments.
  • flame retardant examples include decabromobiphenyl, antimony trioxide, phosphorus flame retardant, aluminum hydroxide and the like.
  • antistatic agent examples include quaternary ammonium salt type cationic surfactants, betaine type amphoteric surfactants, alkyl phosphate type anionic surfactants, primary amine salts, secondary amine salts, thirds.
  • Cationic surfactants such as quaternary amine salts, quaternary amine salts and pyridine derivatives, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, sulfated ester salts of olefins, fatty alcohol sulfate esters, alkyl sulfates
  • Anionic surfactants such as ester salts, fatty acid ethyl sulfonates, alkyl naphthalene sulfonates, alkyl benzene sulfonates, oxalate sulfonates and phosphate ester salts, partial fatty acid esters of polyhydric alcohols, fatty alcohol
  • additives lubricants, fillers, plasticizers, nucleating agents, antiblocking agents, foaming agents, emulsifiers, brighteners, binders, and the like may coexist.
  • the content of the additive is usually 0.1 to 70% by mass, preferably 0.1 to 50% by mass, more preferably 0.5 to 30% in the composition. % By mass, more preferably 2 to 15% by mass.
  • the content of the silicon compound (f) and the solvent (c)) is usually 60% by mass or more, preferably 75% by mass or more, more preferably 85% by mass or more, and still more preferably 95% in the composition. % Or more.
  • Examples of the method of bringing the organosilicon compound (a), the metal alkoxide (b), and the fluorine-containing organosilicon compound (f) into contact with the substrate include, for example, a spin coating method, a dip coating method, a spray coating method, a roll coating method, Examples thereof include a bar coating method and a die coating method, and a spin coating method and a spray coating method are preferable. According to the spin coating method and the spray coating method, the thickness of the film can be easily adjusted.
  • the composition may be further diluted as necessary.
  • the dilution factor is, for example, 2 to 100 times, preferably 5 to 50 times that of the composition before dilution.
  • the solvent illustrated as a solvent (c) can be used suitably.
  • composition of the present invention By leaving the composition of the present invention and the substrate in contact with each other in the air, moisture in the air is taken in and hydrolyzable groups are hydrolyzed to form a siloxane skeleton, thereby forming a film. Is done. When allowed to stand, it may be kept at 40 to 250 ° C.
  • a film formed from the above composition is also included in the scope of the present invention.
  • the coating includes a structure derived from the organosilicon compound (a), the metal alkoxide (b), and the fluorine-containing organosilicon compound (f).
  • the initial contact angle of water ⁇ 01 for the film of the present invention is preferably 80 ° or more, more preferably 90 ° or more, still more preferably 100 ° or more, and may be 140 ° or less. It may be 130 ° or less.
  • the contact angle means a value measured by the ⁇ / 2 method using 3.0 ⁇ L of water.
  • the initial contact angle ⁇ 02 of the oil with respect to the film of the present invention is preferably 55 ° or more, more preferably 60 ° or more, still more preferably 65 ° or more, and may be 120 ° or less. It may be 110 ° or less.
  • the contact angle means a value measured by the ⁇ / 2 method using hexadecane having a liquid volume of 3.0 ⁇ L.
  • the film of the present invention has a contact angle change rate d w2 represented by the following formula of ⁇ 25% or more when the contact angle after immersion in ion exchange water at 70 ° C. for 12 hours is ⁇ w2.
  • a contact angle change rate d w2 represented by the following formula of ⁇ 25% or more when the contact angle after immersion in ion exchange water at 70 ° C. for 12 hours is ⁇ w2.
  • it is -15% or more, more preferably -12% or more, and preferably 0%, but it is also acceptable that it is -1% or less, and further -5% or less.
  • Contact angle change rate d w2 (%) ( ⁇ w2 ⁇ 01 ) / ⁇ 01 ⁇ 100
  • the structure (A) derived from the organosilicon compound (a) is represented by the formula (IA).
  • R a represents a trialkylsilyl group-containing molecular chain
  • Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, a hydrocarbon chain-containing group, or an —O— group.
  • a trialkylsilyl group-containing molecular chain of R a , Z a1 , a siloxane skeleton-containing group of Z a1 , and a hydrocarbon chain-containing group are respectively a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, and a hydrocarbon chain-containing group.
  • the hydrocarbon chain-containing group can be appropriately selected from the range described above.
  • Z a1 is preferably a siloxane skeleton-containing group or an —O— group, and more preferably an —O— group.
  • a structure represented by the formula (IA-I) can be given.
  • the following formulas (IA-I-1) to (IA-I-50) are specific examples of the structure represented by the formula (IA-I), but are not limited thereto.
  • the plurality of R s20 and the plurality of R s10 included therein may be the same or different.
  • the structure (B) derived from the metal alkoxide (b) is represented by the formula (IIB).
  • R b2 represents a hydroxy group or a —O— group.
  • Structure (B) includes a structure represented by the following formula when M is Si.
  • the structure (F) derived from the fluorine-containing organosilicon compound (f) is represented by the formula (IIIF-1) or (IIIF-2).
  • R f1 and R f2 are as defined above.
  • Z f2 represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group, a hydroxy group, or an —O— group.
  • a f3 represents a fluorine-containing alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, or an —O— group.
  • the siloxane skeleton-containing group or a hydrocarbon chain-containing group represented by Z f2, a siloxane skeleton-containing group represented by Z a2, include hydrocarbon chains containing groups and each similar group.
  • Structure (F) includes a structure represented by the following formula.
  • r8 is an integer of 1 to 20, preferably an integer of 1 to 10.
  • r9 is an integer of 1 to 10, preferably an integer of 1 to 5.
  • r10 is an integer of 1 to 10, preferably an integer of 1 to 5.
  • the film formed from the composition of the present invention has a trialkylsilyl group-containing molecular chain and a fluorine-containing group, and has a part that can function as a spacer derived from the metal alkoxide (b). Therefore, both water repellency and oil repellency can be achieved, and the smoothness of the coating surface is also good.
  • a film-treated substrate in which the film of the present invention is formed on the substrate is also included in the scope of the present invention.
  • the shape of the substrate may be either a flat surface or a curved surface, or may be a three-dimensional structure in which a large number of surfaces are combined.
  • the substrate may be composed of any organic material or inorganic material.
  • the organic material examples include acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose Thermoplastic resins such as resins, polyolefin resins, polyvinyl alcohol, etc .; thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, urethane resins; Are ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the metals;
  • the substrate may be subjected to an easy adhesion treatment in advance.
  • the easy adhesion treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment.
  • primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, or the like may be used.
  • the primer layer is preferably a layer formed from a primer layer forming composition containing a component (P) capable of forming a siloxane skeleton (hereinafter sometimes referred to as component (P)).
  • the composition for forming a primer layer comprises a compound represented by the following formula (Pa) as the component (P) (hereinafter sometimes referred to as a compound (Pa)) and / or a partial hydrolysis condensate thereof (P1). It is preferable to include a component.
  • Si (X P2 ) 4 (Pa) [In the formula (Pa), X P2 represents a halogen atom, an alkoxy group or an isocyanate group. ]
  • X P2 is preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms or an isocyanate group, and preferably four X P2 are the same.
  • Si (NCO) 4, Si (OCH 3) 4, Si (OC 2 H 5) 4 and the like are preferable.
  • the (P1) component contained in the primer layer forming composition may be a partial hydrolysis-condensation product of the compound (Pa).
  • the partial hydrolysis-condensation product of compound (Pa) can be produced by a general hydrolysis-condensation method using an acid catalyst or a base catalyst.
  • the degree of condensation (degree of multimerization) of the partially hydrolyzed condensate is preferably such that the product is dissolved in the solvent.
  • the component (Pa) may be a compound (Pa) or a partial hydrolysis condensate of the compound (Pa), and a mixture of the compound (Pa) and its partial hydrolysis condensate, for example, It may be a partially hydrolyzed condensate of the compound (Pa) containing the reaction compound (Pa).
  • a commercial item can also be used as a compound (Pa) and its partial hydrolysis-condensation product.
  • the primer layer forming composition further comprises, as component (P), a compound represented by formula (Pb) (hereinafter sometimes referred to as compound (Pb)) and / or a partially hydrolyzed condensate thereof ( P2) component may be included.
  • component (P) a compound represented by formula (Pb) (hereinafter sometimes referred to as compound (Pb)) and / or a partially hydrolyzed condensate thereof ( P2) component may be included.
  • Pb a compound represented by formula (Pb)
  • P2 a compound represented by formula (Pb)
  • P2 a compound represented by formula (Pb)
  • P2 a partially hydrolyzed condensate thereof
  • examples of the hydrolyzable group represented by X P3 include the same groups or atoms as those of X P2 .
  • X P3 is preferably an alkoxy group or an isocyanate group, and particularly preferably an alkoxy group.
  • the alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.
  • a plurality of X P3 present in the compound (Pb) may be the same group or different groups, and the same group is preferable from the viewpoint of availability.
  • the compound (Pb) one or more kinds can be used, and (CH 3 O) 3 SiCH 2 CH 2 Si (OCH 3 ) 3 , (OCN) 3 SiCH 2 CH 2 Si (NCO) 3 , Cl 3 SiCH 2 CH 2 SiCl 3 , (C 2 H 5 O) 3 SiCH 2 CH 2 Si (OC 2 H 5) 3, (CH 3 O) 3 SiCH 2 CH 2 CH 2 CH 2 CH 2 Si ( OCH 3 ) 3 and the like.
  • Component (P2) may be a partially hydrolyzed condensate of compound (Pb).
  • the partially hydrolyzed condensate of compound (Pb) can be obtained by the same method as described in the production of the partially hydrolyzed condensate of compound (Pa).
  • the degree of condensation (degree of multimerization) of the partially hydrolyzed condensate is preferably such that the product is dissolved in the solvent.
  • Component (P2) may be compound (Pb) or a partial hydrolysis condensate of compound (Pb), and a mixture of compound (Pb) and its partial hydrolysis condensate, for example, It may be a partial hydrolysis-condensation product of the compound (Pb) containing the reaction compound (Pb).
  • the primer layer forming composition may contain a cohydrolysis condensate by cohydrolysis of the compound (Pb) and the compound (Pa) as the component (P), and various polysilazanes are contained. Also good.
  • the composition for forming a primer layer usually contains an organic solvent in consideration of economic efficiency, workability, ease of control of the thickness of the resulting primer layer, etc., in addition to the solid content as a layer constituent component.
  • the organic solvent is preferably one that dissolves the solid content contained in the primer layer forming composition, and examples thereof include the same solvents as the solvent (c) used in the composition.
  • the organic solvent is not limited to one kind, and two or more kinds of solvents having different polarities and evaporation rates may be mixed and used.
  • the composition for primer layer formation contains a partial hydrolysis-condensation product and a partial hydrolysis-condensation product, it may contain the solvent used in order to manufacture these.
  • composition for forming a primer layer even if it does not contain a partial hydrolysis condensate or partial hydrolysis cocondensate, in order to promote the hydrolysis cocondensation reaction, It is also preferable to blend a catalyst such as an acid catalyst that is generally used. Even when a partially hydrolyzed condensate or a partially hydrolyzed cocondensate is included, when the catalyst used for the production thereof does not remain in the composition, it is preferable to add a catalyst.
  • the composition for forming a primer layer may contain water for the above-described components to undergo a hydrolysis condensation reaction or a hydrolysis cocondensation reaction.
  • the base layer forming composition is applied to the surface of the substrate by brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, hand coating, or the like, and is necessary in the air or in a nitrogen atmosphere.
  • the base layer can be formed by curing after drying according to the above. Curing conditions are appropriately controlled depending on the type and concentration of the composition used. In addition, you may perform hardening of the composition for primer layer formation simultaneously with hardening of a composition.
  • the thickness of the primer layer is not particularly limited as long as it can provide moisture resistance, adhesion, and barrier properties such as alkali from the substrate to the film formed thereon.
  • the film formed from the composition of the present invention can achieve both water repellency and oil repellency, adhesion and film-forming properties, display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, etc. It is useful as a base material.
  • the film formed from the composition of the present invention is suitably used as an article such as a body, window glass (front glass, side glass, rear glass), mirror, bumper and the like in transportation equipment such as trains, automobiles, ships, and airplanes. Moreover, it can also be used for outdoor uses, such as a building outer wall, a tent, a solar power generation module, a sound insulation board, and concrete. It can also be used for fishing nets, insect nets, water tanks, and the like.
  • it can be used for various indoor facilities such as kitchens, bathrooms, washstands, mirrors, toilet articles, ceramics such as chandeliers and tiles, artificial marble, and air conditioners. It can also be used as an antifouling treatment for jigs, inner walls, pipes and the like in factories. It is also suitable for goggles, glasses, helmets, slingshots, textiles, umbrellas, play equipment, soccer balls and the like. Furthermore, it can also be used as an anti-adhesive agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.
  • Hot water test The film was immersed in ion exchange water at 70 ° C. for 12 hours, and the contact angle of water before and after immersion was measured. Comprehensive evaluation of the hot water test resistance was performed from the contact angle and change rate after the test.
  • ⁇ Contact angle is 99 ° or more and the change rate of contact angle is ⁇ 10% or more
  • ⁇ Contact angle is less than 99 ° to 90 ° or more, and the contact angle change rate is ⁇ 10% or more
  • ⁇ Contact angle is less than 90 ° Or contact angle change rate is less than -10%
  • Example 1-1 A three-necked flask was charged with 4.69 g of tris (trimethylsiloxy) silanol and 21.0 g of tetrahydrofuran (THF) and stirred. After cooling to ⁇ 40 ° C., 9.38 mL of n-BuLi hexane solution (1.6 mol / L) was added dropwise. The temperature was raised to 0 ° C., 10.01 g of hexamethylcyclotrisiloxane dissolved in 21 g of THF was added dropwise, and the mixture was stirred for 17 hours.
  • THF tetrahydrofuran
  • Example 1-2 A four-necked flask was charged with 0.72 g of trimethylsilanol and 6.72 mL of THF and stirred. After cooling to ⁇ 40 ° C., 5.00 mL of n-BuLi hexane solution (1.6 mol / L) was added dropwise. The temperature was raised to 0 ° C., 14.24 g of hexamethylcyclotrisiloxane dissolved in 16.43 mL of THF was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 17 hours. The mixture was cooled to ⁇ 40 ° C., and 1.59 g of chlorotriethoxysilane was added dropwise. Hexane was added and filtered. The filtrate was concentrated at 13 hPa and 25 ° C. to obtain compound 2. In the formula, the average number of repeating units in parentheses was calculated from the NMR spectrum and found to be 8.
  • Example 2-1 Compound 1 as organosilicon compound (a), tetraethoxysilane (TEOS) as metal alkoxide (b), triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane as fluorine-containing organosilicon compound (f) (C 4 F 9 —C 2 H 4 —Si— (OC 2 H 5 ) 3 ), 0.01 M hydrochloric acid as the catalyst (d), and methyl ethyl ketone (MEK) as the solvent (c) are shown in Table 7. The mixture was mixed at a ratio and stirred for 24 hours to obtain a coating solution.
  • TEOS tetraethoxysilane
  • MEK methyl ethyl ketone
  • a coating solution obtained using a spin coater (manufactured by MIKASA) obtained on an alkali-cleaned glass substrate (EAGLE XG, Corning) was coated at 3000 rpm for 20 s and allowed to stand at room temperature for 1 day. The film was cured at a temperature of
  • Examples 2-2 to 2-8, Comparative Examples 1 to 4 After mixing at a composition ratio shown in Table 9 to obtain a coating solution, a film was obtained in the same manner as in Example 2-1. About the produced membrane
  • Comparative Compound 1 represents a compound represented by the following formula.
  • the average number of repeating units in parentheses was 24 calculated from the NMR spectrum.
  • compositions obtained in the examples were excellent in film forming properties during film formation, and the resulting films were excellent in water and oil repellency, adhesion and film forming properties.
  • all of the compositions obtained in the comparative examples were inferior in film forming properties during film formation.
  • the film obtained from the composition of Comparative Example 4 is inferior in water repellency and oil repellency, and the film obtained from the compositions of Comparative Example 2 and Comparative Example 4 has adhesiveness as a result of the hot water test. I found it inferior.
  • the film formed from the composition of the present invention can achieve both water repellency and oil repellency and film forming properties, and is a base material for display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, etc. Useful as.
  • the film formed from the composition of the present invention is suitably used as an article such as a body, window glass (front glass, side glass, rear glass), mirror, bumper and the like in transportation equipment such as trains, automobiles, ships, and airplanes. Moreover, it can also be used for outdoor uses, such as a building outer wall, a tent, a solar power generation module, a sound insulation board, and concrete. It can also be used for fishing nets, insect nets, water tanks, and the like.
  • it can be used for various indoor facilities such as kitchens, bathrooms, washstands, mirrors, toilet articles, ceramics such as chandeliers and tiles, artificial marble, and air conditioners. It can also be used as an antifouling treatment for jigs, inner walls, pipes and the like in factories. It is also suitable for goggles, glasses, helmets, slingshots, textiles, umbrellas, play equipment, soccer balls and the like. Furthermore, it can also be used as an anti-adhesive agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Paints Or Removers (AREA)
  • Silicon Polymers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition conférant à un revêtement un caractère à la fois hydrofuge et oléofuge et pouvant également améliorer les propriétés de formation de film. La composition de revêtement selon l'invention contient : un composé de silicium organique (a) comprenant, liés à un atome de silicium, au moins une chaîne moléculaire contenant un groupe trialkylsilyle et au moins un groupe hydrolysable ; un alcoxyde métallique (b) ; et un composé de silicium organique contenant du fluor (f) comprenant, liés à un atome de silicium, un groupe contenant du fluor et un groupe hydrolysable. Le composé (a) peut être un composé représenté par la formule (I).
PCT/JP2017/016588 2016-04-28 2017-04-26 Composition Ceased WO2017188331A1 (fr)

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WO2023145301A1 (fr) * 2022-01-31 2023-08-03 住友化学株式会社 Composition mixte, film durci de ladite composition mixte, et verre doté dudit film

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JP2019112540A (ja) * 2017-12-25 2019-07-11 信越化学工業株式会社 有機ケイ素化合物および表面処理剤組成物
JP7135851B2 (ja) * 2018-04-11 2022-09-13 信越化学工業株式会社 撥水性被膜形成用組成物及び撥水性被膜
JP7446840B2 (ja) 2019-04-23 2024-03-11 住友化学株式会社 混合組成物
JP2022094324A (ja) 2020-12-14 2022-06-24 住友化学株式会社 混合組成物

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WO2023145301A1 (fr) * 2022-01-31 2023-08-03 住友化学株式会社 Composition mixte, film durci de ladite composition mixte, et verre doté dudit film

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JP2017201009A (ja) 2017-11-09
CN109071819B (zh) 2021-09-21
TW201809100A (zh) 2018-03-16
TWI721160B (zh) 2021-03-11

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