Classifications

• • 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
• • 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
• • 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
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • 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
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• • 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
  • 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.
• the water / oil repellency of the surface of a substrate such as glass is required to be good. In particular, it is required not only to prevent the droplets from adhering to the surface of the substrate but also to easily remove the adhered droplets.
• Patent Document 1 discloses a coating solution for obtaining a sol-gel film, which has a solid content and a solvent, and the solid content is obtained by hydrolysis and polycondensation of alkoxysilane in an acidic aqueous solution. And a coating solution containing ethylene glycol monoalkyl ether and the acidic aqueous solution as a solvent.
• the alkoxysilane include methyltriethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane.
• Patent Document 2 discloses an example in which an organic silane and a metal alkoxide are mixed at a predetermined ratio, and a solution containing an organic solvent having a vapor pressure larger than that of water, water, and a catalyst is spin-coated on a glass substrate.
• Patent Document 3 discloses that a water-repellent agent containing an amino-modified polysiloxane, an acid, and an activator is further applied by hand spraying with a glass water-repellent agent containing aminosilane.
• Patent Document 4 discloses amino-modified dimethylpolysiloxane and alcohols. It has been disclosed to spray an automotive polishing composition containing water.
• Patent Document 1 does not have water / oil repellency.
• the spin coating method is used in Patent Document 2 and the spray coating method is used in Patent Documents 3 and 4, but special equipment and instruments used in these methods are used.
• the ability to apply the coating by hand without using is very advantageous in terms of cost and simplicity.
• Patent Document 1 discloses a hand-coated film forming method, it is a technique that cannot be said to be simple because it is necessary to wipe off surplus components to finish. Furthermore, the film may be easily destroyed when subjected to friction, etc., and droplets may adhere or become difficult to remove, resulting in problems such as contamination and corrosion of the base material, and further performance degradation. In addition, durability such as wear resistance is also required.
• an object of the present invention is to provide a composition having water repellency, oil repellency, and abrasion resistance and capable of being hand-painted.
• the present invention An organosilicon compound (A1) in which an alkyl group having 6 to 20 carbon atoms, in which a part of a methylene group may be replaced by an oxygen atom, and at least one hydrolyzable group are bonded to a silicon atom, or at least 1
• the molar ratio of the metal compound (B) to the organosilicon compound (A1) or (A2) is preferably 2 or more and 48 or less.
• the organosilicon compound (A1) is preferably represented by the following formula (AI).
• R a1 represents an alkyl group having 6 to 20 carbon atoms in which part of the methylene group may be replaced by an oxygen atom,
• a ⁇ a1> represents a hydrolysable group each independently.
• Z a1 is a hydrocarbon chain-containing group, or represents a hydrolyzable group, and when Z a1 is a hydrocarbon chain containing groups may be the R a1 and Z a1 or different may be the same, Z a1 Is a hydrolyzable group, Z a1 and A a1 may be the same or different.
• R a1 and Z a1 may be the same or different among a plurality of formulas (AI).
• the organosilicon compound (A2) is preferably represented by the following formula (AII).
• R a2 represents a trialkylsilyl group-containing molecular chain, and a plurality of A a2 each independently represents a hydrolyzable group.
• Z a2 represents a trialkylsilyl group-containing molecular chain, a hydrocarbon chain-containing group, a siloxane skeleton-containing group, or a hydrolyzable group.
• the metal compound (B) is preferably represented by the following formula (BI).
• R b1 represents a hydrocarbon chain-containing group or hydrolyzable group in which the maximum chain length of the hydrocarbon chain portion is shorter than the maximum chain length of the alkyl group having 6 to 20 carbon atoms.
• a b1 independently represents a hydrolyzable group.
• M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta.
• m represents an integer of 1 to 4 depending on the valence of M.
• R b1 and A b1 are preferably the same group.
• M is preferably Si.
• an organosilicon compound in which an alkyl group having 6 to 20 carbon atoms and a hydrolyzable group in which a part of a methylene group may be replaced with an oxygen atom is bonded to a silicon atom ( A1) or an organosilicon compound (A2) in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom, and the hydrolyzable group is bonded to a metal atom Coating with water and oil repellency and abrasion resistance on the substrate without unevenness because it contains the metal compound (B), the high boiling point solvent (C), and the low boiling point solvent (D). can do.
• composition of the present invention is an organosilicon in which an alkyl group having 6 to 20 carbon atoms in which a part of a methylene group may be replaced with an oxygen atom and at least one hydrolyzable group are bonded to a silicon atom.
• a metal compound in which a hydrocarbon chain-containing group bonded to an atom and having a maximum chain length of a hydrocarbon chain portion shorter than the maximum chain length of the organosilicon compound (A1) or (A2) may be bonded to the metal atom (B). From such a composition, a hydrolyzable group bonded to a silicon atom or a metal atom is hydrolyzed and polycondensed to form a film.
• the film When (A1) is used as the organosilicon compound, the film has 6 to 20 carbon atoms in which some of the silicon atoms forming the film may be replaced by oxygen atoms with some of the methylene groups.
• An alkyl group (hereinafter sometimes simply referred to as an alkyl group having 6 to 20 carbon atoms) is bonded.
• the film has a water repellent / oil repellent function by the alkyl group having 6 to 20 carbon atoms.
• (A2) as the organosilicon compound, a film having a trialkylsilyl group-containing molecular chain is bonded to a part of the silicon atoms forming the film.
• the trialkylsilyl group imparts water / oil repellency to the film.
• an element to which an alkyl group having 6 to 20 carbon atoms and a trialkylsilyl group are not bonded substantially functions as a spacer in the film, and wear resistance is improved.
• the molar ratio of the organosilicon compound ((A1) or (A2)) to the metal compound (B) is adjusted to a specific range.
• the alkyl group or trialkylsilyl group of several 6 to 20 and the spacer are present in a specific ratio, so that the water and oil repellency functions can be improved and at the same time, a film with further improved wear resistance can be provided. .
• the composition of the present invention contains a high boiling point solvent (C) that satisfies predetermined requirements.
• C a high boiling point solvent
• the composition can be applied evenly with the high-boiling solvent (C) remaining on the substrate without volatilization when the composition is applied to the substrate by hand. It becomes.
• Organosilicon compound (A1) With regard to water / oil repellency, in the present invention, a hydrocarbon chain-containing group (hereinafter referred to as a first hydrocarbon chain-containing group) is bonded to the central silicon atom of the organosilicon compound (A1). It is important that an alkyl group having 6 to 20 carbon atoms is bonded to a silicon atom as the hydrocarbon chain-containing group.
• the alkyl group having 6 to 20 carbon atoms imparts water / oil repellency to the resulting film interface (surface). In particular, the coefficient of friction between the droplets (water droplets, oil droplets, etc.) and the film is reduced, and the droplets are easy to move.
• the alkyl group having 6 to 20 carbon atoms described above preferably has 7 to 17 carbon atoms, and more preferably 8 to 15 carbon atoms.
• a first hydrocarbon chain-containing group may be further bonded.
• the first hydrocarbon chain-containing group (including an alkyl group having 6 to 20 carbon atoms) is usually composed of only a hydrocarbon group (hydrocarbon chain), but if necessary, a part of the hydrocarbon chain
• the methylene group (—CH 2 —) may be replaced with an oxygen atom. Even a group partially substituted with an oxygen atom in this manner is classified as a hydrocarbon chain-containing group because a hydrocarbon chain exists in the remaining part.
• the methylene group (—CH 2 —) adjacent to the Si atom is not replaced with an oxygen atom, and two consecutive methylene groups (—CH 2 —) are not replaced with an oxygen atom at the same time.
• the first hydrocarbon chain-containing group will be described using an oxygen-unsubstituted alkyl group and a hydrocarbon chain-containing group (that is, a monovalent hydrocarbon group) as an example.
• a part of the methylene group (—CH 2 —) can be replaced with an oxygen atom.
• the first hydrocarbon chain-containing group which may be further bonded in addition to the alkyl group having 6 to 20 carbon atoms.
• the group preferably has 6 to 20 carbon atoms, more preferably 7 to 17 carbon atoms, and still more preferably 8 to 15 carbon atoms. It is.
• the carbon number of these groups means the number of carbons before being replaced with oxygen atoms.
• the first hydrocarbon chain-containing group (in the case of a hydrocarbon group) containing an alkyl group having 6 to 20 carbon atoms may be branched or linear.
• the first hydrocarbon chain-containing group (in the case of hydrocarbon group) which may be further bonded is a saturated or unsaturated aliphatic hydrocarbon chain-containing group.
• it is a saturated aliphatic hydrocarbon chain-containing group.
• the saturated aliphatic hydrocarbon chain-containing group is more preferably a saturated aliphatic hydrocarbon group.
• alkyl group having 6 to 20 carbon atoms and the saturated aliphatic hydrocarbon group examples include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group. , Hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
• the saturated aliphatic hydrocarbon group is preferred as the hydrocarbon group.
• the group in which a methylene group (—CH 2 —) as a part of the hydrocarbon group is replaced with an oxygen atom specifically includes a group having a (poly) ethylene glycol unit, Examples include a group having a (poly) propylene glycol unit.
• the number of the first hydrocarbon chain-containing groups bonded to the central silicon atom is usually 1 or more including the number of alkyl groups having 6 to 20 carbon atoms, and 2 or less. It is particularly preferable that the number is 1 (that is, only the alkyl group having 6 to 20 carbon atoms as the first hydrocarbon chain-containing group).
• the hydrolyzable group of the organosilicon compound (A1) may be any group that provides a hydroxy group (silanol group) by hydrolysis.
• the number of carbon atoms is 1 such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.
• Preferred examples thereof include an alkoxy group of 1 to 4, a hydroxy group, an acetoxy group, a chlorine atom, an isocyanate group, and the like.
• 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 usually 1 or more, preferably 2 or more, and usually 3 or less.
• the silicon atom of the organosilicon compound (A1) has fewer carbon atoms in the hydrocarbon chain portion than the alkyl group having 6 to 20 carbon atoms and hydrolyzable group, and the alkyl group having 6 to 20 carbon atoms.
• a hydrocarbon chain-containing group (hereinafter referred to as a second hydrocarbon chain-containing group) may be bonded.
• the length of the alkyl group having 6 to 20 carbon atoms and the second hydrocarbon chain-containing group is the length of the longest straight chain (hereinafter also referred to as “main chain”) containing an element bonded to a metal atom such as Si. It can be evaluated as (longest chain length).
• the hydrocarbon chain moiety has 6 to 20 carbon atoms. It is preferable that it is less than carbon number of the alkyl group of.
• the second hydrocarbon chain-containing group is composed of only a hydrocarbon group (hydrocarbon chain) as in the case of the alkyl group having 6 to 20 carbon atoms.
• the methylene group (—CH 2 —) may be a group in which an oxygen atom is replaced. Further, the methylene group (—CH 2 —) adjacent to the Si atom is not replaced with an oxygen atom, and two consecutive methylene groups (—CH 2 —) are not replaced with an oxygen atom at the same time.
• 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.
• the number of carbon atoms is assumed assuming that the oxygen atom is a methylene group (—CH 2 —).
• the second hydrocarbon chain-containing group will be described by taking an oxygen non-substituted hydrocarbon chain-containing group (that is, a monovalent hydrocarbon group) as an example. Part of the group (—CH 2 —) can be replaced with an oxygen atom.
• the number of carbon atoms is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less. Further, the second hydrocarbon chain-containing group (in the case of a hydrocarbon group) may be branched or linear.
• the second 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 (in the case of a hydrocarbon group) is more preferably a saturated aliphatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.
• the hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and a partial methylene group (— Specific examples of the group in which CH 2 —) is replaced by an oxygen atom include a group having a (poly) ethylene glycol unit.
• the number of the second hydrocarbon chain-containing groups bonded to the central silicon atom is preferably 2 or less, more preferably 1 or less, and particularly preferably 0.
• the organosilicon compound (A1) is preferably a compound represented by the following formula (AI).
• R a1 represents an alkyl group having 6 to 20 carbon atoms in which part of the methylene group may be replaced by an oxygen atom, and a plurality of A a1 are independently hydrolyzable.
• Z a1 is a hydrocarbon chain-containing group, or represents a hydrolyzable group, and when Z a1 is a hydrocarbon chain containing groups may be the R a1 and Z a1 or different may be the same, Z a1 Is a hydrolyzable group, Z a1 and A a1 may be the same or different.
• R a1 and Z a1 may be the same or different among a plurality of formulas (AI).
• the second hydrocarbon chain-containing group and the hydrolyzable group can be appropriately selected from the ranges described above.
• Z a1 is preferably a second hydrocarbon chain-containing group or a hydrolyzable group, and more preferably a hydrolyzable group.
• organosilicon compound (A1) a compound having one alkyl group having 6 to 20 carbon atoms and three hydrolyzable groups; one alkyl group having 6 to 20 carbon atoms and a second hydrocarbon Preferred examples include compounds having one chain-containing group and one hydrolyzable group.
• the three hydrolyzable groups are bonded to a silicon atom.
• the group in which three hydrolyzable groups are bonded to a silicon atom include trialkoxysilyl groups such as a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, and a tributoxysilyl group; a trihydroxysilyl group; Acetoxysilyl group; trichlorosilyl group; triisocyanatesilyl group; and the like.
• one second hydrocarbon chain-containing group, and two hydrolyzable groups one second hydrocarbon chain-containing group, two The hydrolyzable group is bonded to the silicon atom.
• the group in which one second hydrocarbon chain-containing group and two hydrolyzable groups are bonded to a silicon atom include methyldimethoxysilyl group, ethyldimethoxysilyl group, methyldiethoxysilyl group, ethyldiethoxysilyl group Group, alkyl dialkoxysilyl group such as methyldipropoxysilyl group; and the like.
• the compound having one alkyl group having 6 to 20 carbon atoms and three hydrolyzable groups include alkyltrimethoxysilane having an alkyl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms.
• An alkyltrialkoxysilane having an alkyl group having 6 to 20 carbon atoms such as an alkyltriethoxysilane having an alkyl group of 6; an alkyltrihydroxysilane having an alkyl group having 6 to 20 carbon atoms; an alkyl group having 6 to 20 carbon atoms;
• specific examples of the compound having one alkyl group having 6 to 20 carbon atoms, one second hydrocarbon chain-containing group, and two hydrolyzable groups include 6 to 20 carbon atoms.
• Alkylmethyldialkoxysilanes such as alkylmethyldimethoxysilane having an alkyl group and alkylmethyldiethoxysilane having an alkyl group having 6 to 20 carbon atoms; alkylmethyldihydroxysilane having an alkyl group having 6 to 20 carbon atoms; Alkylmethyldiacetoxysilane having an alkyl group of ⁇ 20; alkylmethyldichlorosilane having an alkyl group of 6 to 20 carbon atoms; alkylmethyl diisocyanate silane having an alkyl group of 6 to 20 carbon atoms; and the like.
• a compound having one alkyl group having 6 to 20 carbon atoms and three hydrolyzable groups is preferable, and an alkyltrialkoxysilane having an alkyl group having 6 to 20 carbon atoms is more preferable.
• Organosilicon compound (A2) 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.
• organosilicon compound (A2) a compound in which one trialkylsilyl group-containing molecular chain and three hydrolyzable groups are bonded to a central silicon atom; one trialkylsilyl group-containing molecular chain, 1 Compound in which one siloxane skeleton-containing group and two hydrolyzable groups are bonded to the central silicon atom; one trialkylsilyl group-containing molecular chain, one hydrocarbon chain-containing group, and two hydrolyzable groups A compound in which the group is bonded to the central silicon atom;
• the organosilicon compound (A2) is preferably a compound represented by the following formula (AII).
• R a2 represents a trialkylsilyl group-containing molecular chain, and a plurality of A a2 each independently represents a hydrolyzable group.
• Z a2 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 and physical durability are enhanced, 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 / oil repellency of 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. Even in such a case, the trialkylsilyl group-containing molecular chain has a trialkylsilyl 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, the remainder is a dialkylsiloxane chain, so that the resulting film has good chemical and physical durability.
• 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 and 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 , Z s1 , Y 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 , Z s1 , Y 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 number of molecular chains containing a trialkylsilyl group 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 a methoxy group, an ethoxy group, a propoxy group, and a butoxy group Preferred examples include 1-4 alkoxy groups; hydroxy groups; acetoxy groups; chlorine atoms; isocyanate groups.
• 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 elements than the number of elements 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.
• the total number of atoms of the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, and preferably 10 or more.
• the difference in the number of atoms between the trialkylsilyl group-containing molecular chain and the siloxane skeleton-containing group is preferably 10 or more, more preferably 20 or more, and preferably 1000 or less, more preferably 500 or less. More preferably, it is 200 or less.
• 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—, It is preferably composed of only hydrogen 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 (A2) is preferably a compound represented by the following formula (I-1), and more preferably a compound represented by the formula (I-1-1).
• a a2 , Z a2 , Z s1 , Y s1 , R s2 , R s3 , and n1 are as defined above.
• the organosilicon compound (A2) may be a compound represented by the formula (I-2), preferably a compound represented by the formula (I-2-1).
• a a2 , Z a2 , Z s1 , Y s1 , R s2 , R s3 , and n1 are as defined above.
• organosilicon compound (A2) examples include a group represented by the formula (II).
• Examples of the synthesis method of the organosilicon compound (A2) 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 (A2) is prepared by reacting, for example, alkali metal silyl oxide 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 number of silicon atoms contained in the cyclic dimethylsiloxane is, for example, preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, and further preferably 2 or more and 4 or less.
• the organosilicon compound (A2) can be prepared by, for example, reacting an alkali metal silyl oxide and a cyclic dimethylsiloxane and reacting the resulting hydroxyl-terminated dimethylsiloxane compound with a tetraalkoxysilane. Can also be manufactured.
• the metal compound (B) contained in the composition together with the organosilicon compound (A1) or (A2) is one in which at least one hydrolyzable group is bonded to a central metal atom, and the second hydrocarbon A chain-containing group may be bonded to the metal atom.
• the longest chain length of the second hydrocarbon chain-containing group is shorter than the longest chain length of the alkyl group having 6 to 20 carbon atoms bonded to the central silicon atom of the organosilicon compound (A1). Since it is shorter than the trialkylsilyl group-containing molecular chain bonded to the central silicon atom of A2), the longest chain length of the metal compound (B) is shorter than the longest chain length of the organosilicon compound.
• the structure derived from the metal compound (B) is less bulky than the structure derived from the organosilicon compound (A1) or (A2), and the film obtained by including the metal compound (B) in the composition It is possible to form a part having a spacer function in.
• the central metal atom of the metal compound (B) may be any metal atom that can be bonded to an alkoxy group to form a metal alkoxide.
• the metal includes a semimetal such as Si or Ge.
• Specific examples of the central metal atom of the metal compound (B) include trivalent metals such as Al, Fe, and In; tetravalent metals such as Ge, Hf, Si, Ti, Sn, and Zr; pentavalent metals such as Ta. And the like, preferably trivalent metals such as Al; tetravalent metals such as Si, Ti, Zr and Sn; more preferably Al, Si, Ti and Zr, still more preferably Si. is there.
• hydrolyzable group of the metal compound (B) examples include the same hydrolyzable groups as those of the organosilicon compound (A1) or (A2), preferably an alkoxy group having 1 to 4 carbon atoms, An alkoxy group of ⁇ 2 is more preferred. Further, the hydrolyzable groups of the organosilicon compound (A1) and the metal compound (B) may be the same or different. Further, the hydrolyzable groups of the organosilicon compound (A1) and the metal compound (B) are preferably alkoxy groups having 1 to 4 carbon atoms. In the metal compound (B), the number of hydrolyzable groups is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 4 or less.
• the second hydrocarbon chain-containing group of the metal compound (B) can be appropriately selected from the range described above, and the number thereof is preferably 1 or less, and particularly preferably 0.
• the metal compound (B) is preferably a compound represented by the following formula (BI).
• R b1 represents a second hydrocarbon chain-containing group or a hydrolyzable group.
• a b1 independently represents a hydrolyzable group.
• M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta.
• m represents an integer of 1 to 4 depending on the metal atom.
• the range the second hydrocarbon chains containing group, R b1, hydrolysable groups A b1 of R b1 are respectively, the above-described second hydrocarbon chains containing group, a hydrolyzable group Can be selected as appropriate.
• R b1 is preferably a hydrolyzable group.
• R b1 and A b1 may be the same or different and are preferably the same.
• the hydrolyzable groups of the organosilicon compound (A1) and the metal compound (B) may be the same or different.
• M is preferably Al, Si, Ti, Zr, or Sn, more preferably Al, Si, Ti, or Zr, and even more preferably Si.
• These alkoxides of metal atoms can be easily liquefied, and it is easy to improve the uniformity of the distribution of the following structure (b) that can function as a spacer in the film.
• m represents 2 when M is a trivalent metal such as Al, Fe, or In, and M is a tetravalent metal such as Ge, Hf, Si, Ti, Sn, or Zr.
• Preferred examples of the metal compound (B) include a compound having only a hydrolyzable group; a compound having one second hydrocarbon chain-containing group and two hydrolyzable groups;
• Examples of the compound having only a hydrolyzable group include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; trialkoxyaluminums such as triethoxyaluminum, tripropoxyaluminum, and tributoxyaluminum; triethoxy Trialkoxy iron such as iron; trialkoxy indium such as trimethoxy indium, triethoxy indium, tripropoxy indium and tributoxy indium; tetraalkoxy germanium such as tetramethoxy germanium, tetraethoxy germanium, tetrapropoxy germanium and tetrabutoxy germanium; tetra Methoxy hafnium, tetraethoxy hafnium, tetrapropoxy hafnium, tetrabut Tetraalkoxy hafnium such as Si
• Examples of the compound having a second hydrocarbon chain-containing group and a hydrolyzable group include alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and methyltripropoxysilane; And alkenyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane.
• the organosilicon compound (A1) or (A2) and the metal compound (B) are contained in a specific ratio, the water and oil repellency functions are improved and the wear resistance is improved. It is possible to provide a film having excellent properties.
• the molar ratio of the metal compound (B) to the organosilicon compound (A1 or A2) (metal compound (B) / organosilicon compound (A1 or A2)) is 2 or more. (More preferably 15 or more), preferably 48 or less, more preferably 44 or less, still more preferably 40 or less, and particularly preferably 36 or less.
• the composition of the present invention further contains a high boiling point solvent (C) in addition to the organosilicon compound (A1) or (A2) and the metal compound (B).
• a high boiling point solvent (C) in addition to the organosilicon compound (A1) or (A2) and the metal compound (B).
• the high boiling point solvent (C) remains on the substrate without volatilization, so that the organosilicon compound (A1) or (A2) and the metal compound (B) are on the substrate. It is possible to achieve a film with good water and oil repellency and wear resistance and good surface properties.
• the high boiling point solvent (C) means that the vapor pressure at 20 ° C. is 1000 Pa or less and the boiling point is 120 ° C. or more.
• a high-boiling solvent having a solubility parameter within a predetermined range in consideration of compatibility with the low-boiling solvent (D) ( C) must be used.
• the solubility parameter SP value, solubility parameter
• a high boiling point solvent (C) having an SP value [(cal / cm 3 ) 1/2 ] of 8.0 or more is used.
• the SP value [(cal / cm 3 ) 1/2 ] of the high boiling point solvent (C) is preferably 13.0 or less.
• the solvent satisfying such requirements include 1-butanol and ethylene glycol monohexyl ether.
• the vapor pressure of the high boiling point solvent (C) at 20 ° C. is preferably 800 Pa or less, more preferably 600 Pa or less, and the lower limit is not particularly limited, but is, for example, 5 Pa.
• the boiling point of the high-boiling solvent (C) is preferably 150 ° C. or higher, more preferably 170 ° C. or higher, and the upper limit is not particularly limited, but is, for example, 300 ° C.
• composition of the present invention further contains a low boiling point solvent (D) in addition to the organosilicon compound (A), metal compound (B), and high boiling point solvent (C).
• Low boiling point means that the vapor pressure at 20 ° C. is more than 1000 Pa and the boiling point is less than 120 ° C.
• Examples of such a low boiling point solvent (D) include alcohol solvents, ketone solvents, ether solvents, and alicyclic hydrocarbon solvents, and alcohol solvents, ketone solvents, and ether solvents are particularly preferable.
• the alcohol solvent include methanol, ethanol, 1-propanol, isopropyl alcohol, 2,2,2-trifluoroethanol, 2-butanol, and isobutyl alcohol.
• the ketone solvent include acetone and ethyl methyl ketone.
• Examples of the ether solvent include diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether and the like. Hexane is mentioned as an alicyclic hydrocarbon type solvent.
• the vapor pressure at 20 ° C. of the low boiling point solvent (D) is preferably 2000 Pa or more, more preferably 3000 Pa or more, and the upper limit is not particularly limited, but is, for example, 13000 Pa.
• the boiling point of the high boiling point solvent (D) is preferably 100 ° C. or lower, more preferably 85 ° C. or lower.
• the high boiling point solvent (C) and the low boiling point solvent (D) may be used alone or in combination of two or more solvents.
• an organosilicon compound (A) and a metal compound (B) are mixed into a mixed liquid obtained by previously mixing a part of the low boiling point solvent (D) with the high boiling point solvent (C).
• a solution for example, stirring at room temperature for about 10 to 30 minutes
• the dilution ratio with the low boiling point solvent (D) is preferably about 5 to 40 times.
• the composition of the present invention may or may not contain a solvent other than the high boiling point solvent (C) and the low boiling point solvent (D) (hereinafter sometimes referred to as other solvent).
• the organosilicon compound (A) (hereinafter, the organosilicon compounds (A1) and (A2) may be collectively referred to as an organosilicon compound (A)) is 0.01% relative to the low boiling point solvent (D).
• the content is preferably 0.15% by mass, more preferably 0.03-0.13% by mass.
• the metal compound (B) is preferably 0.1 to 1.2% by mass, more preferably 0.15 to 1.0% by mass with respect to the low boiling point solvent (D).
• the high boiling point solvent (C) is preferably 0.05 to 1.8% by mass, more preferably 0.1 to 1.8% by mass with respect to the low boiling point solvent (D). 5 mass% or less may be sufficient, and 1.2 mass% or less may be sufficient.
• the organosilicon compound (A) is 0.03 to 0.15% by mass with respect to 100% by mass in total of the high boiling point solvent (C), the low boiling point solvent (D), the other solvent and the catalyst (E) described later. It is preferable that the content is 0.035 to 0.12% by mass.
• the metal compound (B) is 0.1 to 1.5% by mass relative to 100% by mass in total of the high boiling point solvent (C), the low boiling point solvent (D), the other solvent and the catalyst (E) described later. It is preferably 0.15 to 1.2% by mass.
• the total ratio of the organosilicon compound (A) and the metal compound (B) to the total 100 mass% of the high boiling point solvent (C), the low boiling point solvent (D), the other solvent and the catalyst (E) described later is ((A + B) / (C + D + E)), preferably 0.13 to 1.65% by mass, more preferably 0.185 to 1.32% by mass, and still more preferably 0.2 to 1.1% by mass.
• composition of the present invention may coexist with a catalyst (E) as necessary.
• the catalyst (E) can be arbitrarily selected from acid catalysts such as hydrochloric acid, formic acid and acetic acid generally used in the sol-gel method; base catalysts; organometallic catalysts and the like.
• the acid catalyst (particularly preferably hydrochloric acid) is preferably 1 or more times, more preferably 1.3 or more times in terms of mass ratio with respect to the total of the organosilicon compound (A) and the metal compound (B). It is preferably 8 times or less, more preferably 7 times or less, and still more preferably 6.5 times or less.
• organosilicon compound (A) and the metal compound (B) are brought into contact with the base material
• other solvents high boiling point solvent (C) and low boiling point solvent (D) may be used as long as the effects of the present invention are not impaired.
• Solvents not equivalent to any of the above antioxidants, rust inhibitors, UV absorbers, light stabilizers, fungicides, antibacterial agents, biofouling inhibitors, deodorants, pigments, flame retardants, antistatic agents, etc. These various additives may coexist.
• 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.
• examples include acid di-n-octadecyl ester and tetrakis (3-dodecylthiopropionic acid) pentaerythritol ester.
• 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'-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
• pigments examples include carbon black, titanium oxide, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, perylene or perinone 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 additives is usually 0.1 to 70% by mass, preferably 0.1% in the composition containing the organosilicon compound (A) and the metal compound (B). -50% by mass, more preferably 0.5-30% by mass, still more preferably 2-15% by mass.
• the total content of the organosilicon compound (A) and the metal compound (B) is 0.1% with respect to a total of 100% by mass of the high boiling point solvent (C), the low boiling point solvent (D), and the catalyst (E).
• the content is preferably 1.5% by mass, more preferably 0.15-1.2% by mass.
• the composition of the present invention comprises one alkyl group having 7 to 9 carbon atoms (particularly 8) and an organosilicon compound (A1) in which three hydrolyzable groups are bonded to a silicon atom.
• the weight ratio (metal compound (B) / organosilicon compound (A)) to organosilicon compound (A) is 5 or more (more preferably 15 or more) and 36 or less.
• the composition of the present invention can be brought into contact with the substrate evenly by hand coating, and hydrolyzable groups of the organosilicon compound (A) and the metal compound (B) are hydrolyzed and polycondensed to form a surface on the substrate surface. A film is formed.
• the hand coating evaluation in the present invention the following method is adopted to reproduce a state close to actual use. First, two pseudo fingers (mono-one dust catch made by Dragonfly Co.) were placed on the bencott, attached to a steel wool tester (made by Daiei Seiki Co., Ltd.), and 1 ml of the coating solution 1 was immersed in the bencott.
• the composition when the composition is left in contact with the substrate in the air (for example, about 10 to 48 hours), moisture in the air is taken in, and hydrolysis and polycondensation of the hydrolyzable group occurs. This is preferable because it is promoted.
• the obtained film may be further dried.
• the temperature for heating and drying is usually 40 to 250 ° C, preferably 60 to 200 ° C, more preferably 60 to 150 ° C.
• the obtained film has a network skeleton in which silicon atoms or the above metal atoms (preferably only silicon atoms) are bonded through oxygen atoms. And having a structure in which the first hydrocarbon chain-containing group is bonded to some of the silicon atoms forming the skeleton, derived from the organosilicon compound (A1).
• the structure in which the alkyl group having 6 to 20 carbon atoms is bonded to the silicon atom is preferably a structure (a1) represented by the following formula (1).
• R a3 represents an alkyl group having 6 to 20 carbon atoms
• Z a3 represents a hydrocarbon chain-containing group or —O— group
• Z a3 represents a hydrocarbon chain-containing group.
• the R a3 and Z a3 may be the same or different and is an R a3 and Z a3 among multiple expressions (1) may be the same or different.
• all of the first hydrocarbon chain-containing groups of Z a3 are the first hydrocarbon chain-containing groups described above (including alkyl groups having 6 to 20 carbon atoms), the first hydrocarbon chain It can select suitably from the range of a containing group.
• the second hydrocarbon chain-containing group or —O— group is preferable, and —O— group is particularly preferable.
• structures represented by the following formulas (1-1) to (1-32) can be preferably exemplified.
• a silicon atom (second silicon atom) derived from the metal compound (B) and different from the silicon atom to which the alkyl group having 6 to 20 carbon atoms is bonded.
• a second hydrocarbon chain-containing group, a hydroxy group, an alkoxy group, or a group in which a hydroxy group is condensed may be bonded.
• the second silicon atom may be replaced by another metal atom (for example, Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta).
• These second silicon atoms and other metal atoms are also bonded to a second hydrocarbon chain-containing group, hydroxy group, alkoxy group, or hydroxy group having a shorter chain length than the alkyl group having 6 to 20 carbon atoms. Therefore, it acts as a spacer, and it is possible to enhance the water / oil repellency improving effect by the alkyl group having 6 to 20 carbon atoms.
• the alkoxy group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.
• a butoxy group, a propoxy group, an ethoxy group, a methoxy group, etc. are mentioned.
• hydroxy group is condensed with other hydroxy groups, alkoxy groups and the like to form —O—, and such a condensed group of hydroxy groups may be bonded to the metal atom.
• the structure in which the second hydrocarbon chain-containing group or hydroxy group is bonded to the second silicon atom or other metal atom is preferably a structure (b) represented by the following formula (2).
• R b2 represents a second hydrocarbon chain-containing group or a hydroxy group, and A b2 represents a hydroxy group or —O—.
• M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta.
• n represents an integer of 0 to 3 according to M.
• any of the second hydrocarbon chain-containing groups of R b2 can be appropriately selected from the range described above.
• R b2 is preferably a hydroxy group.
• M is preferably a trivalent metal such as Al; a tetravalent metal such as Si, Ti, Sn, or Zr; more preferably Al, Si, Ti, or Zr, and particularly preferably Si.
• n represents 1 when M is a trivalent metal such as Al, Fe, or In, and M is a tetravalent metal such as Ge, Hf, Si, Ti, Sn, or Zr. Represents 2 and represents 3 when M is a pentavalent metal such as Ta.
• the abundance ratio of the structure (a) to the structure (b) (structure (a) / structure (b)) is preferably 0.01 or more on a molar basis, more preferably 0.8. 02 or more, more preferably 0.03 or more, preferably 0.3 or less, more preferably 0.2 or less, still more preferably 0.1 or less, and still more preferably 0.09 or less.
• the structure (a2) derived from the organosilicon compound (A2) is represented by the formula (3).
• R a4 represents a trialkylsilyl group-containing molecular chain
• Z a4 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, a hydrocarbon chain-containing group, or —O—.
• R a4 , Z a4 trialkylsilyl group-containing molecular chain, Z a4 siloxane skeleton-containing group, and hydrocarbon chain-containing group are respectively a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group,
• the hydrocarbon chain-containing group can be appropriately selected from the range described above.
• Z a4 is preferably a siloxane skeleton-containing group or —O—, and more preferably —O—.
• Structure (a2) includes a structure represented by formula (3-1).
• the structure (b) derived from the metal compound (B) is the same as when the organosilicon compound (A1) is used.
• the film obtained using the composition of the present invention usually has a thickness of about 3 to 50 nm.
• the film obtained using the composition of the present invention has a network-like skeleton in which silicon atoms or the above metal atoms (preferably only silicon atoms) are bonded through oxygen atoms. Since it has a structure in which the alkyl group having 6 to 20 carbon atoms is bonded to some of the silicon atoms to be formed, it is excellent in the slipperiness of the droplets, and also in the water and oil repellency.
• the water repellency can be evaluated by, for example, the contact angle of a 3 ⁇ L water droplet determined by the ⁇ / 2 method, and the contact angle is, for example, 97 ° or more, more preferably 100 ° or more, and further preferably 101 ° or more.
• the upper limit is not particularly limited, but is 110 °, for example.
• the slipperiness of the droplet can be evaluated by, for example, the sliding angle or contact angle hysteresis of the droplet deposited on the substrate.
• the sliding angle of a 6 ⁇ L liquid droplet is preferably 23 ° or less, more preferably 21 ° or less, still more preferably 20 ° or less, and the lower limit is, for example, 5 °.
• the contact angle hysteresis is preferably 8.0 ° or less, more preferably 7 ° or less, still more preferably 6 ° or less, and the lower limit is, for example, 1.0 °.
• a film can be formed by coating the composition of the present invention on a substrate, and the shape of the substrate may be flat or curved.
• the substrate may be composed of any organic material or inorganic material.
• the organic material include acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose Thermoplastic resins such as resins and polyolefin resins; thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, urethane resins; and the like
• inorganic materials include ceramics Glass; metal such as iron, silicon, copper, zinc, and aluminum; alloy containing the metal; and the like.
• 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.
• a film having both water and oil repellency and abrasion resistance can be provided by hand coating, and it can be suitably used for various types of vehicles and building windows.
• Example 1-1 Triethoxy-n-octylsilane (octyltriethoxysilane) 2.2 ⁇ 10 ⁇ 4 mol as the organosilicon compound (A1), tetraethyl orthosilicate (tetraethoxysilane) 3.5 ⁇ 10 ⁇ as the metal compound (B) 3 mol was dissolved in a mixed solution of 0.95 ml of isopropyl alcohol and 0.95 ml of 1-butanol and stirred at room temperature for 20 minutes. To the obtained solution, 1.0 ml of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was dropped, and then stirred for 24 hours to prepare a sample solution. The sample solution was diluted 30 times with isopropyl alcohol to obtain a coating solution 1-1.
• the coating solution 1 is soaked in Bencott (Asahi Kasei Co., Ltd. clean room wiper, registered trademark), coated on an alkali-cleaned glass substrate (5 cm ⁇ 5 cm, Corning “EAGLE XG”), and allowed to stand at room temperature for one day. I put it. Coating was performed by the following method. Two pseudo fingers (mono-one dust catch made by Dragonfly) were placed on the bencott, attached to a steel wool tester (made by Daiei Seiki Co., Ltd.), and 1 ml of the coating solution 1 was immersed in the bencott.
• the initial static and dynamic contact angles, wear resistance, and haze of the prepared coatings were evaluated. Further, as sensory evaluation, water droplet slipping property and visual observation of the film surface were performed.
• Example 1-2 A coating solution 1-2 was prepared in the same manner as in Example 1-1 except that the ratio of 1-butanol in the coating solution was set to the value shown in Table 7-1. Similarly, a film was prepared and evaluated.
• Example 1-3 A coating solution 1-3 was prepared in the same manner as in Example 1-1 except that the ratio of 1-butanol in the coating solution was set to the value shown in Table 7-1. Similarly, a film was prepared and evaluated.
• Example 2-1 Triethoxy-n-octylsilane (octyltriethoxysilane) 2.2 ⁇ 10 ⁇ 4 mol as the organosilicon compound (A1), tetraethyl orthosilicate (tetraethoxysilane) 3.5 ⁇ 10 ⁇ as the metal compound (B) 3 mol was dissolved in a mixed solution of 1.8 ml of isopropyl alcohol and 0.095 ml of ethylene glycol monohexyl ether, and stirred at room temperature for 20 minutes.
• Example 1-1 1.0 ml of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst (E) was dropped, and then stirred for 24 hours to prepare a sample solution.
• the sample solution was diluted 30 times with isopropyl alcohol to obtain a coating solution 2-1. Otherwise, a film was prepared and evaluated in the same manner as in Example 1-1.
• Example 2-2 A coating solution 2-2 was prepared in the same manner as in Example 2-1, except that the ratio of ethylene glycol monohexyl ether in the coating solution was as shown in Table 7-1. A film was prepared in the same manner as in Example 1 and evaluated.
• Example 3-1 Triethoxy-n-decylsilane (decyltriethoxysilane) 1.8 ⁇ 10 ⁇ 4 mol as the organosilicon compound (A1), tetraethyl orthosilicate (tetraethoxysilane) 3.7 ⁇ 10 ⁇ 3 as the metal compound (B) Mol was dissolved in a mixed solution of 1.0 ml of isopropyl alcohol and 1.0 ml of 1-butanol and stirred at room temperature for 20 minutes. To the obtained solution, 1.1 ml of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was dropped, and then stirred for 24 hours to prepare a sample solution. The sample solution was diluted 30 times with isopropyl alcohol to obtain a coating solution 3-1. Otherwise, a film was prepared and evaluated in the same manner as in Example 1-1.
• Example 3-2 Coating solution as in Example 3-1, except that triethoxy-n-dodecylsilane (dodecyltriethoxysilane) was used in place of triethoxy-n-decylsilane (decyltriethoxysilane) as the organosilicon compound (A1) 3-2 was prepared, and a film was prepared and evaluated in the same manner as in Example 1-1.
• Example 3-3 The sample solution was diluted 50-fold with isopropyl alcohol to give a coating solution 3-3, which was the same as Example 3-2.
• Example 4 Triethoxy-n-octylsilane (octyltriethoxysilane) 1.2 ⁇ 10 ⁇ 3 mol as organosilicon compound (A1), silicate 40 as metal compound (B) 6.0 ⁇ 10 ⁇ 3 mol in isopropyl It was dissolved in a mixed solution of 5.1 ml of alcohol and 5.1 ml of 1-butanol and stirred at room temperature for 20 minutes. To the obtained solution, 5.4 ml of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was dropped, and then stirred for 24 hours to prepare a sample solution. The sample solution was diluted 30 times with isopropyl alcohol to obtain a coating solution 4. Thereafter, a film was prepared and evaluated in the same manner as in Example 1-1.
• Example 5 Triethoxy-n-octylsilane (octyltriethoxysilane) 2.2 ⁇ 10 ⁇ 4 mol as the organosilicon compound (A1) and tetraethyl orthosilicate 3.5 ⁇ 10 ⁇ 3 mol as the metal compound (B) were mixed with isopropyl. It was dissolved in a mixed solution of 0.89 ml of alcohol and 0.95 ml of 1-butanol and stirred at room temperature for 20 minutes. A film was prepared and evaluated in the same manner as in Example 1-1 except that 2.1 mL of formic acid (1 mol / L aqueous solution) was used instead of 1.0 mL of hydrochloric acid as the catalyst (E). went.
• Example 6 Example of synthesis of alkoxysilane compound> A three-necked flask was charged with 4.69 g of tris (trimethylsiloxy) silanol and 21.0 g of 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.
• organosilicon compound (A2) 1.4 ⁇ 10 ⁇ 4 mol of the alkoxysilane compound represented by the above formula, and 1.4 ⁇ 10 ⁇ 3 mol of tetraethyl orthosilicate as the metal compound (B) are mixed with isopropyl alcohol 6 It was dissolved in a mixed solution of 7 ml and 1-butanol 2.0 ml and stirred at room temperature for 20 minutes. A film was prepared in the same manner as in Example 1-1, except that 2.8 mL of hydrochloric acid (0.01 mol / L aqueous solution) as the catalyst (E) was added dropwise to the resulting solution and stirred for 24 hours. Evaluation was performed.
• Comparative Example 1 Instead of the organosilicon compound (A), 3.59 g of methyltriethoxysilane and 10.92 g of tetraethyl orthosilicate (tetraethoxysilane) as the metal compound (B) are dissolved in 5.03 g of ethylene glycol monobutyl ether, and at room temperature. Stir for 20 minutes. To the obtained solution, 10.46 g of acetic acid (0.5 mol / L aqueous solution) as a catalyst was dropped, and then stirred for 24 hours to obtain a coating solution a. Using this coating solution a, a glass substrate was coated by hand in the same manner as in Example 1-1, and allowed to stand at room temperature for 1 day to produce a film and evaluated.
• acetic acid 0.5 mol / L aqueous solution
• Comparative Example 2 2.8 g of triethoxy-n-octylsilane (octyltriethoxysilane) as the organosilicon compound (A) and 4.6 g of tetramethyl orthosilicate (tetramethoxysilane) as the metal compound (B) are dissolved in 1.7 g of ethanol. And stirred at room temperature for 20 minutes. To the obtained solution, 0.28 g of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was dropped, and then stirred for 24 hours to obtain a coating solution b. Using this coating solution b, a glass substrate was coated by hand in the same manner as in Example 1-1, and allowed to stand at room temperature for 1 day to produce a film and evaluated.
• a glass substrate was coated by hand in the same manner as in Example 1-1, and allowed to stand at room temperature for 1 day to produce a film and evaluated.
• Comparative Example 4-2 A coating solution d-2 was prepared in the same manner as in Comparative Example 4-1, except that 0.095 ml of dimethyl sulfoxide was used instead of methyl ethyl ketone. Using this coating solution d-2, a glass substrate was coated by hand in the same manner as in Example 1-1, and allowed to stand at room temperature for 1 day to produce a film and evaluated.
• Comparative Example 5 A coating solution e was prepared in the same manner as in Comparative Example 4-2, except that 0.095 ml of n-octane was used instead of dimethyl sulfoxide. Using this coating solution e, a glass substrate was coated by hand in the same manner as in Example 1-1, and allowed to stand at room temperature for 1 day to produce a film and evaluated.
• Comparative Example 6 A coating solution f was prepared in the same manner as in Comparative Example 5 except that dodecane was used instead of octane. Using this coating solution f, a glass substrate was coated by hand in the same manner as in Example 1-1, and allowed to stand at room temperature for 1 day to produce a film and evaluated.
• Comparative Example 7 A coating solution g was prepared in the same manner as in Comparative Example 6 except that 1,2 dimethoxyethane was used instead of dodecane. Using this coating solution g, a glass substrate was coated by hand in the same manner as in Example 1-1, and allowed to stand at room temperature for 1 day to produce a film and evaluated.
• Table 10 shows the vapor pressure and boiling point of various solvents at 20 ° C.

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