WO2019189791A1 - Mixed composition - Google Patents

Mixed composition Download PDF

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Publication number
WO2019189791A1
WO2019189791A1 PCT/JP2019/014073 JP2019014073W WO2019189791A1 WO 2019189791 A1 WO2019189791 A1 WO 2019189791A1 JP 2019014073 W JP2019014073 W JP 2019014073W WO 2019189791 A1 WO2019189791 A1 WO 2019189791A1
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Prior art keywords
group
solvent
composition
compound
mass
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PCT/JP2019/014073
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French (fr)
Japanese (ja)
Inventor
彩香 櫻井
真芳 ▲徳▼田
泰治 島崎
Original Assignee
住友化学株式会社
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Priority to CN201980022412.6A priority Critical patent/CN111918927A/en
Priority to KR1020207031030A priority patent/KR20200138780A/en
Publication of WO2019189791A1 publication Critical patent/WO2019189791A1/en

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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • 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
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes

Definitions

  • the present invention relates to a mixed composition of an organosilicon compound and a metal compound.
  • Patent Document 1 discloses a solution containing an organic silane such as an alkylalkoxysilane having 3 to 18 carbon atoms, a metal alkoxide, an organic solvent, water, and a catalyst.
  • organic solvent include methanol, ethanol, isopropanol, tetrahydrofuran and the like whose vapor pressure is higher than that of water.
  • Patent Document 2 satisfies at least one of an organosilicon compound, a metal compound, a vapor pressure at 20 ° C. of 1000 Pa or less, and a boiling point of 120 ° C. or more, and a solubility parameter of 8.
  • the water-repellent film may be exposed to harsh environments such as ultraviolet rays and rainwater depending on applications such as outdoors, and it is preferable that good performance can be maintained even after being exposed to harsh environments.
  • harsh environments such as ultraviolet rays and rainwater depending on applications such as outdoors
  • good performance can be maintained even after being exposed to harsh environments.
  • an organosilicon compound is used for a water-repellent film
  • the stability to light is very high.
  • siloxane bond since it has been found that it is not easy to have durability against water and warm water. It was. Therefore, in order to maintain good performance even after being exposed to a harsh environment in a water-repellent film having an organosilicon compound, a film having a high temperature resistance to water can be used in an actual use environment. It can be said that this is an important performance to maintain.
  • Patent Document 2 discloses an organosilicon compound having a trialkylsilyl group-containing molecular chain as the organosilicon compound, and the total amount of the organosilicon compound and the metal compound is about 0. 0% with respect to 100% by mass of the composition. Although it is about 3%, it is desired to further increase the total amount of the organosilicon compound and the metal compound in consideration of the adhesion of the film. According to the study by the present inventors, it has been found that in the composition of Patent Document 2, when the concentrations of the organosilicon compound and the metal compound are increased, durability against warm water (warm water resistance) tends to deteriorate.
  • the present invention provides a composition having a high total concentration of an organosilicon compound having a trialkylsilyl group-containing molecular chain and a metal compound, and capable of forming a film having good warm water resistance.
  • the purpose is to provide.
  • the present inventors have found that the above-mentioned problems can be achieved and completed the present invention.
  • the present invention is as follows.
  • the hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom,
  • the total amount of the organosilicon compound (a) and the metal compound (b) in the composition is 0.5% by mass or more,
  • the mixed composition, wherein the amount of the solvent (c2) in the composition is 5% by mass or more.
  • R a1 represents a trialkylsilyl group-containing molecular chain
  • a ⁇ a1> represents a hydrolysable group each independently
  • Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group
  • a hydrogen atom contained in the trialkylsilyl group in R a1 and Z a1 may be substituted with a fluorine atom, and x is 0 or 1.
  • a ⁇ a1> represents a hydrolysable group each independently
  • Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group
  • a hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom
  • a plurality of R s1 each independently represents a hydrocarbon group or a trialkylsilyloxy group, and a hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group may be substituted with a fluorine atom
  • a plurality of R s2 each independently represents an alkyl group having 1 to 10 carbon atoms
  • Z s1 represents —O— or a divalent hydrocarbon group, and —CH 2 — contained in the
  • Y s1 represents a single bond or —Si (R s2 ) 2 —L s1 —, the L s1 represents a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group is -O- may be substituted.
  • n1 represents an integer of 1 or more, x is 0 or 1.
  • the obtained film has good hot water resistance as evaluated by the sliding speed after the hot water test.
  • the composition of the present invention is obtained because the organosilicon compound (a) and the metal compound (b) are not less than 0.5% by mass in total and the solvent (c2) satisfying the predetermined requirements is mixed.
  • the resulting film has good hot water resistance, and preferably the film can have good transparency.
  • the organosilicon compound (a), the metal compound (b), and the solvent (c2) will be described in order.
  • the said mixed composition contains the thing which reaction advanced, for example during storage after mixing.
  • Organosilicon compound (a) In the organosilicon compound (a) in the present invention, at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group may be referred to as a silicon atom (hereinafter, this silicon atom may be referred to as “central silicon atom”). ).
  • 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 of the film formed from the mixed composition of the invention is improved. Further, the presence of the trialkylsilyl group-containing molecular chain reduces the resistance between the droplet (water droplet or the like) and the film, and the droplet easily moves. Even when the alkyl group of the trialkylsilyl-containing group is replaced with a fluoroalkyl group, the water repellency at the film interface (surface) can be improved in the same manner.
  • the number of trialkylsilyl group-containing molecular chains bonded to the central silicon atom is 1 or more, preferably 3 or less, more preferably 2 or less, and particularly preferably 1 It is.
  • the hydrolyzable group may be a group that gives a hydroxy group by hydrolysis (to form a silanol group by bonding with a silicon atom), and examples thereof include carbon such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • Preferred examples include an alkoxy group of 1 to 6; a hydroxy group; an acetoxy group; a chlorine atom; an isocyanate group; Among these, an alkoxy group having 1 to 6 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is further preferable.
  • the number of hydrolyzable groups bonded to the central silicon atom is 1 or more, preferably 2 or more, and usually 3 or less.
  • the central silicon atom of the organosilicon compound (a) includes a siloxane skeleton-containing group (preferably the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain) A siloxane skeleton-containing group having a smaller number of elements), or a hydrocarbon chain-containing group (preferably a hydrocarbon chain having a hydrocarbon chain having fewer carbon atoms than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain) A chain-containing group) may be bonded.
  • the organosilicon compound (a) is preferably a compound represented by the following formula (A1).
  • R a1 represents a trialkylsilyl group-containing molecular chain, a plurality of A a1 each independently represents a hydrolyzable group, Z a1 represents a trialkylsilyl group-containing molecular chain, It represents a siloxane skeleton-containing group or a hydrocarbon chain-containing group, the hydrogen atom contained in the trialkylsilyl group in R a1 and Z a1 may be substituted with a fluorine atom, and x is 0 or 1.
  • R a1 is a trialkylsilyl group-containing molecular chain and is a monovalent group having a structure in which a trialkylsilyl-containing group is bonded to the end of the molecular chain as described above.
  • 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).
  • each of the plurality of R s1 independently represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group is substituted with a fluorine atom. It may be. * Represents a bond. In the above formula (s1), or that at least one trialkyl silyl group of R s1, it is preferred that R s1 are all alkyl groups.
  • R s1 is a hydrocarbon group
  • the carbon number thereof is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
  • R s1 is a hydrocarbon group
  • an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable.
  • 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.
  • the total number of carbon atoms of the three R s1 is preferably 9 or less, more preferably 6 or less, and even more preferably 4 or less. 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.
  • R s1 is 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).
  • two or more R s1 are preferably a trialkylsilyloxy group, and more preferably three R s1 are a trialkylsilyloxy 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-containing group In a trialkylsilyl group-containing molecular chain, the trialkylsilyl-containing group must be bonded to the end (free end side) of the molecular chain, particularly the end of the main chain (longest straight chain) (free end side). Is preferred.
  • the molecular chain to which the trialkylsilyl-containing 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 containing a dialkylsiloxane 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 each independently represents an alkyl group having 1 to 10 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.
  • R s2 preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and still more preferably 1 to 2.
  • N1 is preferably 1 to 100, more preferably 1 to 80, still more preferably 1 to 60, still more preferably 1 to 45, 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.
  • q1 represents an integer of 1 to 60
  • * represents a bond bonded to a central silicon atom or a trialkylsilyl-containing group.
  • q1 can be in the same numerical range as n1, and is preferably an integer of 1 to 30.
  • the total number of elements constituting the trialkylsilyl group-containing molecular chain is preferably 24 or more, more preferably 40 or more, and still more preferably 50 or more. Further, it is preferably 5000 or less, more preferably 4000 or less, still more preferably 2000 or less, even more preferably 1200 or less, still more preferably 700 or less, and particularly preferably 250 or less.
  • the trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s3).
  • R s1 , R s2 , Z s1 , Y s1 , and n1 are as defined above. * Represents a bond with the central silicon atom.
  • the trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s3-1) or (s3-2), and preferably a group represented by the following formula (s3-2). Is more preferable.
  • trialkylsilyl group-containing molecular chain is represented by the following formula (s3-1), it is more preferably a group represented by the following formula (s3-1-1).
  • R s2 , Y s1 , Z s1 , and n1 have the same meanings as described above.
  • R s3 represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond with the central silicon atom.
  • the number of carbon atoms of the alkyl group represented by R s3 is preferably 1 to 3, more preferably 1 to 2.
  • the total carbon number of R s3 contained in * -Si (R s3 ) 3 is preferably 9 or less, more preferably 6 or less, more preferably 4 or less.
  • 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.
  • trialkylsilyl group-containing molecular chain is represented by the following formula (s3-2), it is more preferably a group represented by the following formula (s3-2-1).
  • R s2 , Y s1 , Z s1 , and n1 have the same meanings as described above.
  • R s4 represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond with the central silicon atom.
  • Examples of the trialkylsilyl group-containing molecular chain include a group represented by the formula (s3-I).
  • * represents a bond with the central silicon atom.
  • n10 is preferably 1 to 30.
  • a a1 in the formula (A1) will be described.
  • a plurality of A a1 are each independently a hydrolyzable group and may be any group that gives a hydroxy group (silanol group) by hydrolysis.
  • carbon such as methoxy group, ethoxy group, propoxy group, butoxy group, etc.
  • Preferred examples include an alkoxy group having 1 to 4; a hydroxy group; an acetoxy group; a chlorine atom; an isocyanate group; 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.
  • Z a1 in the formula (A1) represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group.
  • Z a1 is a trialkylsilyl group-containing molecular chain, the same as the above R a1 can be mentioned.
  • the siloxane skeleton-containing group is a monovalent group containing a siloxane unit (Si—O—), and constitutes a trialkylsilyl group-containing molecular chain of R a1. It is preferable that the number of elements is smaller than the number of elements to be formed. As a result, 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 (s4).
  • R s2 , Z s1 , and Y s1 have the same meanings 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.
  • n3 represents an integer of 0 to 5. * Represents a bond with the central 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.
  • N3 is preferably 1 to 5, and more preferably 1 to 3.
  • the total number of elements of the siloxane skeleton-containing group is preferably 600 or less, more preferably 500 or less, further preferably 350 or less, still more preferably 100 or less, still more preferably 50 or less, and particularly preferably 30 or less. Moreover, it is preferable that it is 10 or more.
  • the difference in the number of elements between the molecular chain containing R a1 trialkylsilyl group and the group containing Z a1 siloxane skeleton is preferably 10 or more, more preferably 20 or more, and preferably 1000 or less. More preferably, it is 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 portion has a smaller number of carbon atoms than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain.
  • the number of carbon atoms of the longest straight chain of the hydrocarbon chain is preferably smaller than the number of elements constituting the longest straight chain of the trialkylsilyl group-containing molecular chain.
  • the hydrocarbon chain-containing group is usually composed only of a hydrocarbon group (hydrocarbon chain), but if necessary, a group in which a part of the methylene group (—CH 2 —) of the hydrocarbon chain is replaced with an oxygen atom. It may be. 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 —).
  • 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.
  • an oxygen-nonsubstituted hydrocarbon chain-containing group that is, a monovalent hydrocarbon group
  • the methylene group — Part of CH 2 —
  • oxygen atoms can be replaced with oxygen atoms.
  • the number of carbon atoms is preferably 1 or more and 3 or less, more preferably 1. Further, the hydrocarbon chain-containing group may be branched or linear.
  • the hydrocarbon chain-containing 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 more preferably a saturated aliphatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, and a propyl group.
  • X in the formula (A1) is 0 or 1, preferably 0.
  • the hydrolyzable group represented by A a1 gives a hydroxy group by hydrolysis as described above as the hydrolyzable group possessed by the organosilicon compound (a) (bonded to a silicon atom to form a silanol group). ) Group, and those exemplified above can be employed.
  • the organosilicon compound (a) represented by the formula (A1) is preferably a compound represented by the following formula (A2).
  • R s1 , R s2 , Z s1 , Y s1 , n1, A a1 , Z a1 , and x are as defined above.
  • the organosilicon compound (a) represented by the above formula (A2) is preferably represented by the following formula (A2-1) or the following formula (A2-2), and is represented by the following formula (A2-2). More preferably.
  • organosilicon compound (a) represented by the above formula (A2) is represented by the following formula (A2-1), it is more preferably a compound represented by the formula (A2-1-1).
  • R s2 , R s3 , Y s1 , Z s1 , n1 and A a1 are as defined above.
  • organosilicon compound (a) represented by the above formula (A2) is a compound represented by the following formula (A2-2), it is a compound represented by the following formula (A2-2-1) Is more preferable.
  • R s2 , R s4 , Y s1 , Z s1 , n1 and A a1 are as defined above.
  • organosilicon compound (a) represented by the above formula (A2) include compounds represented by the formula (AI).
  • N10 in (AI-1) to (AI-25) in Table 3-1 are all preferably 1 to 30.
  • N10 in (AI-26) to (AI-50) in Table 3-2 are all preferably 1 to 30.
  • each of n10 in (AI-51) to (AI-100) is preferably 1 to 30.
  • the organosilicon compound (a) represented by the formula (A2) is preferably a compound represented by the following formula.
  • n10 is 1 to 60, preferably 1 to 50, more preferably 1 to 30.
  • Examples of the method for synthesizing the organosilicon compound (a) include a method described in JP-A-2017-201109.
  • the amount of the organosilicon compound (a) is, for example, 0.2% by mass or more, more preferably 0.3% by mass or more, and preferably 3.0% by mass or less, in 100% by mass of the composition. Preferably it is 2.0 mass% or less.
  • the amount of the above-mentioned organosilicon compound (a) it is preferable that either the blending amount at the time of preparing the composition or the value calculated from the analysis result of the composition satisfies the above range.
  • the value calculated from the blending amount at the time of preparation of the composition and the analysis result of the composition is the same as above. It is preferable that either satisfies the range.
  • the mixed composition of the present invention may use two or more organic silicon compounds (a).
  • the organosilicon compound (a) may be a condensate in the composition.
  • the metal compound (b) is a compound in which at least one hydrolyzable group is bonded to a metal atom (hereinafter sometimes referred to as a metal atom M).
  • the metal atom M of the metal compound (b) may be any metal atom that can be bonded to an alkoxy group to form a metal alkoxide, and the metal atom in this specification includes a semimetal such as Si or Ge.
  • Specific examples 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.
  • Metal is preferred. More preferred are trivalent metals such as Al or tetravalent metals such as Si, Ti, Zr and Sn, still more preferred are Al, Si, Ti and Zr, and most preferred is Si.
  • hydrolyzable group of the metal compound (b) examples include the same hydrolyzable groups as mentioned for the organosilicon compound (a), preferably an alkoxy group having 1 to 4 carbon atoms, more preferably carbon It is an alkoxy group of the number 1 or 2.
  • the hydrolyzable groups of the organosilicon compound (a) and the metal compound (b) may be the same or different, but both are preferably alkoxy groups having 1 to 4 carbon atoms.
  • a siloxane skeleton-containing group (which may be bonded to the central silicon atom of the organosilicon compound (a)) may be bonded to a bond other than the bond to which the hydrolyzable group is bonded (
  • a siloxane skeleton-containing group having an element number smaller than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain of the organosilicon compound (a); and bonded to the central silicon atom of the organosilicon compound (a)
  • a hydrocarbon chain-containing group (preferably containing a hydrocarbon chain having a number of carbon atoms smaller than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain of the organosilicon compound (a).
  • a hydrogen atom may be bonded, and can be appropriately selected from the range described in the organosilicon compound (a), and the number of bonds is preferably 1 or less, particularly
  • the number of hydrolyzable groups is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or less.
  • a compound having only a hydrolyzable group a compound having a siloxane skeleton-containing group and a hydrolyzable group; a compound having two siloxane skeleton-containing groups and a hydrolyzable group; containing a hydrocarbon chain
  • a compound having a group and a hydrolyzable group a compound having two hydrocarbon chain-containing groups and a hydrolyzable group
  • a compound having a hydrogen atom and a hydrolyzable group a hydrogen atom, a hydrocarbon chain-containing group and a hydrolyzable group
  • Examples thereof include a compound having a group.
  • 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, tributoxy indium; tetraalkoxy hafnium such as tetramethoxy hafnium, tetraethoxy hafnium, tetrapropoxy hafnium, tetrabutoxy hafnium; tetra; Tetraal such as methoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium Tetraal
  • Examples of the compound having a siloxane skeleton-containing group and a hydrolyzable group include trimethylsilyloxytrialkoxysilane such as trimethylsilyloxytrimethoxysilane, trimethylsilyloxytriethoxysilane, and trimethylsilyloxytripropoxysilane.
  • Examples of the compound having two siloxane skeleton-containing groups and hydrolyzable groups include di (trimethylsilyloxy) such as di (trimethylsilyloxy) dimethoxysilane, di (trimethylsilyloxy) diethoxysilane, and di (trimethylsilyloxy) dipropoxysilane. Dialkoxysilane; and the like.
  • Examples of the compound having a hydrocarbon chain-containing group and a hydrolyzable group include alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and methyltripropoxysilane; vinyltrimethoxy Alkenyl trialkoxysilanes such as silane and vinyltriethoxysilane; Examples of the compound having two hydrocarbon chain-containing groups and a hydrolyzable group include dialkyl dialkoxysilanes such as dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, and diethyldiethoxysilane.
  • Examples of the compound having a hydrogen atom and a hydrolyzable group include trimethoxysilane, triethoxysilane, and tripropoxysilane.
  • Examples of the compound having a hydrogen atom, a hydrocarbon chain-containing group, and a hydrolyzable group include dimethoxymethylsilane and diethoxymethylsilane.
  • the metal compound (b) is preferably a compound represented by the following formula (B1).
  • M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta
  • Z b1 represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group or a hydrogen atom
  • a ⁇ b1> represents a hydrolysable group each independently, m represents an integer of 3 to 5, depending on the metal atom, r is 0 or 1;
  • Siloxane skeleton-containing groups in Z b1 in the formula (B1), the hydrocarbon chain-containing group, and hydrolyzable groups A b1 is the organic silicon compound (a) siloxane skeleton-containing group described in, hydrocarbon chains containing A group and a hydrolyzable group can be appropriately selected, and preferred ranges are also the same.
  • m represents an integer of 3 to 5, depending on the metal atom, that is, the valence of the metal atom M.
  • r is preferably 0.
  • M is Si
  • r is 0, and
  • a b1 is preferably an alkoxy group having 1 to 4 carbon atoms, that is, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is Tetramethoxysilane or tetraethoxysilane is particularly preferable.
  • the amount of the metal compound (b) is, for example, 0.3% by mass or more, more preferably 0.5% by mass or more, and preferably 5% by mass or less in 100% by mass of the composition, more preferably 3%. It is below mass%.
  • the mixed composition of the present invention may use two or more metal compounds (b). Further, the metal compound (b) may be a condensate in the composition.
  • the total amount of the organosilicon compound (a) and the metal compound (b) is 0.5% by mass or more, preferably 0.8% by mass or more, more preferably 100% by mass. 1.0 mass% or more, 5 mass% or less is preferable, More preferably, it is 4 mass% or less, More preferably, it is 3 mass% or less.
  • the molar ratio of the metal compound (b) to the organosilicon compound (a) ((b) / (a)) is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more, and 40 or less. Is more preferably 35 or less, and still more preferably 30 or less.
  • Solvent 3-1 Solvent (c2)
  • the vapor pressure of the solvent (c2) at 20 ° C. is from 0.032 kPa to 10 kPa, and the sp value is 11 (cal / cm 3 ) 1/2 or less.
  • such a solvent (c2) is mixed in an amount of 5% by mass or more in the composition.
  • the solvent (c2) having such characteristics is characterized by having good compatibility with components such as the organosilicon compound (a) and the metal compound (b), and that it evaporates moderately when deposited. is there. With this feature, the film composition distribution of the resulting film becomes appropriate, and the remaining solvent is reduced, so that the warm water resistance can be improved.
  • the vapor pressure (20 ° C.) of the solvent (c2) is preferably 0.05 kPa or more, more preferably 0.1 kPa or more, and preferably 8 kPa or less, more preferably 6 kPa or less.
  • the vapor pressure is 6 kPa or less, the appearance of the film is improved, and the sliding property immediately after the film formation is also improved.
  • the sliding speed at the time can be 10 mm / second or more.
  • the sp value of the solvent (c2) is 11 (cal / cm 3 ) 1/2 or less.
  • sp value Solubility Parameter, solubility parameter
  • RF Fedors Polym. Eng. Sci., 14 [2], 147-154 (1974)”. It is.
  • the sp value is defined by the square root of the cohesive energy density. Specifically, the sp value is defined by the following equation.
  • ⁇ ( ⁇ E / V) 1/2 (1)
  • ⁇ means the sp value ((cal / cm 3 ) 1/2 )
  • ⁇ E means the cohesive energy (cal / mol)
  • V means the molar molecular volume (cm 3 / mol) of the solvent.
  • butyl acetate used as the preferred solvent (c2) in the present invention is a solvent having two —CH 3 , three —CH 2 —, and one —COO—.
  • the sp value of the solvent (c2) is preferably 10.5 (cal / cm 3 ) 1/2 or less, more preferably 10 (cal / cm 3 ) 1/2 or less, and 5 (cal / cm 3 ). 3 ) 1/2 or more is preferable, more preferably 6 (cal / cm 3 ) 1/2 or more.
  • the boiling point of the solvent (c2) at atmospheric pressure is, for example, 85 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and preferably 190 ° C. or lower, more preferably 180 ° C. or lower. .
  • solubility of water at 20 ° C. in the solvent (c2) is, for example, 230 g / L or less, and the lower limit is not particularly limited, but may be 1 g / L or more.
  • Examples of the solvent (c2) include isopropyl acetate, butyl acetate, 2-ethoxyethyl acetate and the like.
  • the amount of the solvent (c2) is 5% by mass or more with respect to 100% by mass of the composition, and the warm water resistance of the film obtained in this way is improved.
  • the amount of the solvent (c2) is preferably 23.0% by mass or more, and by doing so, the warm water resistance can be further improved.
  • the amount of (c2) is more preferably 30% by mass or more, further preferably 40% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more.
  • the upper limit is, for example, 98% by mass or less.
  • the amount of the solvent (c2) is preferably 55% by mass or more because the appearance of the film can be improved.
  • the mixed composition of the present invention may use two or more solvents (c2).
  • the composition of the present invention has a water solubility at 20 ° C. of 231 g / in with the solvent (c2). It is preferable that a solvent (c1) having an L value of not less than L and an sp value of not more than 20 is mixed.
  • the solubility of water at 20 ° C. of the solvent (c1) is preferably 250 g / L or more, more preferably 300 g / L or more, and the upper limit is not particularly limited, and the solvent (c1) and water are mixed at an arbitrary ratio. Preferably it can be done.
  • the sp value of the solvent (c1) is preferably 18 (cal / cm 3 ) 1/2 or less, more preferably 16 (cal / cm 3 ) 1/2 or less, and 11 (cal / cm 3 ) 1/2. It is preferable that it is super.
  • the boiling point of the solvent (c1) at atmospheric pressure is, for example, less than 85 ° C., preferably 83 ° C. or less, and the lower limit is, for example, 60 ° C. or more.
  • Examples of the solvent (c1) include isopropanol, ethanol, methanol, and methyl ethyl ketone.
  • the amount of the solvent (c1) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, and preferably 50% by mass or less with respect to 100% by mass of the composition. More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less.
  • the mass ratio (c2 / c1) of the solvent (c2) to the solvent (c1) is preferably 1 or more, more preferably 3 or more, still more preferably 10 or more, and preferably 45 or less, more preferably 40. It is as follows.
  • solvent (c1) When the solvent (c1) is mixed in the composition of the present invention, two or more solvents (c1) may be used.
  • the composition of the present invention may be mixed with any of an acid catalyst, a base catalyst, and an organometallic catalyst that are generally used in the sol-gel method.
  • the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; and organic acids such as citric acid, oxalic acid, and acetic acid.
  • the base catalyst include ammonia and amines.
  • organometallic catalyst examples include organometallic compounds having a metal element such as Al, Fe, Zn, Sn, and Zr as a central metal, and organoaluminum compounds such as aluminum acetylacetone complex and aluminum ethylacetoacetate complex; iron octylate and the like Organic zinc compounds such as zinc acetylacetonate monohydrate, zinc naphthenate and zinc octylate; organic tin compounds such as dibutyltin diacetate complex;
  • the catalyst is preferably an acid catalyst, particularly an organic acid catalyst such as acetic acid.
  • the amount of the catalyst is, for example, 0.1 to 0.5% by mass in 100% by mass of the composition.
  • the composition of the present invention may be mixed with water, and the amount of water can be arbitrarily selected as long as it can be uniformly dissolved in a solvent. For example, it is preferable that it is 0.5 mass% or less in 100 mass% of compositions. By appropriately controlling the amount of water, it can be expected that the uniformity of the reaction solution is improved and the reproducibility of preparation is improved.
  • the amount of water is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and may be 0.01% by mass or more.
  • the ratio of water to the total of 100 parts by mass of the solvents (c1) and (c2) is preferably 0.01 parts by mass or more. 0.3 mass part or less is preferable.
  • the amount of water is preferably adjusted with respect to the total amount of the organosilicon compound (a) and the metal compound (b), and the mole of water relative to the total molar amount of the organosilicon compound (a) and the metal compound (b).
  • the ratio of the amount is preferably 0.1 or more, more preferably 0.12 or more, further preferably 0.2 or more, and preferably 10 or less, more preferably 5 or less, still more preferably 3 or less. Yes, particularly preferably 2 or less.
  • composition of the present invention is an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-bioadhesive agent, a deodorant and a pigment as long as the effects of the present invention are not impaired
  • additives such as a flame retardant and an antistatic agent may be mixed.
  • the preparation procedure of the mixed composition of the present invention is as follows. First, the organosilicon compound (a) and the metal compound (b) are dissolved in a solvent. At this time, it is preferable to stir for about 5 to 30 minutes. Subsequently, if necessary, a catalyst (preferably an acid catalyst) is added, followed by stirring for 1 to 24 hours (preferably stirring while heating at about 40 to 70 ° C.). In this way, some of the hydrolyzable groups contained in the organosilicon compound (a) and the metal compound (b) are hydrolyzed by moisture in the air or moisture contained in the catalyst used as necessary. Causes decomposition and dehydration condensation reactions.
  • a catalyst preferably an acid catalyst
  • reaction solvent As the solvent for dissolving the organosilicon compound (a) and the metal compound (b) (hereinafter sometimes referred to as “reaction solvent”), it is preferable to use the solvent (c1) described above.
  • (C1) A uniform solution can be prepared by using a solvent. Furthermore, the said solvent (c2) is added and diluted to the obtained solution, and a coating solution (mixed composition of this invention) is produced. By mixing the solvent (c2) with the coating solution, the volatilization of the solvent after coating on the substrate can be appropriately adjusted, and the transparency and warm water resistance of the resulting film are improved. As long as the solvent (c2) is mixed, the diluting solvent may be mixed with another solvent, and the diluting solvent may be a mixture of the solvent (c2) and the solvent (c1).
  • Examples of the method of bringing the mixed composition of the present invention into contact with the substrate include a method of coating the substrate with the composition, such as spin coating, dip coating, spray coating, roll coating, bar coating.
  • Method, hand-coating a method of soaking a liquid in a cloth and applying to a base material
  • pouring a method of applying the liquid as it is to a base material using a dropper, etc.
  • spraying a base material using a spray
  • room temperature for example, 0.5 to 48 hours, preferably 10 to 48 hours
  • heat for about 1 to 10 hours.
  • the film thickness of the film formed from the mixed composition of the present invention can be, for example, about 0.5 to 100 nm, although it depends on the coating method.
  • the contact angle of water droplets evaluated by the method of Examples described later for the film is, for example, 95 ° to 110 ° (preferably 98 ° to 108 °).
  • the haze of the film evaluated by the method of Examples described later is, for example, 1.4% or less, preferably 1.0% or less, more preferably 0.8% or less, and further preferably 0. .6% or less, particularly preferably 0.3% or less. Although a minimum is not specifically limited, For example, it is about 0.01%.
  • the contact angle of water droplets in the film after the hot water test evaluated by the method described later is, for example, 95 ° to 113 ° (preferably 98 ° to 110 °).
  • the sliding speed of the film after the hot water test is, for example, 5 mm / second or more, preferably 10 mm / second or more, more preferably 15 mm / second or more, further preferably 20 mm / second or more, and the upper limit. Is not particularly limited, but is, for example, 100 mm / second or less.
  • the substrate to which the mixed composition of the present invention is contacted is not particularly limited, and 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 material of the base material is not limited and may be composed of either an organic material or an inorganic material.
  • organic material examples include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, and polyolefin resin; phenol resin, urea resin, melamine resin, epoxy resin,
  • inorganic materials include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the above metals; etc. Is mentioned.
  • 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.
  • primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, or the like may be performed, or a glass film such as polysilazane may be applied to the substrate in advance.
  • Example 1 In the above formula (AI-26), 0.29 g of the compound (1) having an average value of n10 of 24 and 0.71 g of tetraethoxysilane were dissolved in 2.13 g of isopropanol. To the obtained solution, 0.0008 g of acetic acid as a catalyst and 0.14 g of water were dropped, and then stirred at 65 ° C. for 4 hours to prepare a sample solution. The sample solution 1 was diluted with 66.88 g of butyl acetate to obtain a coating solution 1.
  • the coating solution 1 is formed on a non-alkali glass (Eagle XG) that has been plasma-treated by a spin coater (manufactured by MIKASA) under the conditions of a rotational speed of 3000 rpm and 20 seconds, and then heat treated at 200 ° C. for 3 hours to obtain a sample. It was.
  • a spin coater manufactured by MIKASA
  • Example 2 A film was formed on the substrate in the same manner as in Example 1 except that the coating solution 2 was prepared by diluting the sample solution with 74.10 g of 2-ethoxyethyl acetate.
  • Example 3 The same as in Example 1, except that the stirring time in the preparation of the sample solution was 6 hours and the sample solution was diluted with a mixed solution of 23.74 g of isopropanol and 44.46 g of 2-ethoxyethyl acetate to prepare the coating solution 3. Thus, a film was formed on the substrate.
  • Example 4 The same as in Example 1, except that the stirring time for the preparation of the sample solution was 6 hours and the sample solution was diluted with a mixed solution of 11.87 g of isopropanol and 59.28 g of 2-ethoxyethyl acetate to prepare the coating solution 4. Thus, a film was formed on the substrate.
  • Example 5 In the above formula (AI-26), 0.21 g of the compound (1) having an average value of n10 of 24 and 0.53 g of tetraethoxysilane were dissolved in 1.49 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0008 g of acetic acid as a catalyst and 0.14 g of water were dropped, and then stirred at room temperature for 4 hours to prepare a sample solution. The sample solution was diluted with 55.58 g of 2-ethoxyethyl acetate to obtain a coating solution 5. The coating solution 5 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
  • Example 6 The same as in Example 5 except that the stirring time for the preparation of the sample solution was 6 hours, and the coating solution 6 was prepared by diluting the sample solution with a mixed solution of 8.90 g of isopropanol and 44.46 g of 2-ethoxyethyl acetate. Thus, a film was formed on the substrate.
  • Example 7 In the above formula (AI-26), 0.22 g of compound (1) having an average value of n10 of 24 and 0.55 g of tetraethoxysilane were dissolved in 1.34 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0008 g of acetic acid as a catalyst and 0.14 g of water were dropped, and then stirred at room temperature for 6 hours to prepare a sample solution. The sample solution was diluted with 55.58 g of 2-ethoxyethyl acetate to obtain a coating solution 7. The coating solution 7 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
  • Example 8 In the above formula (AI-26), 0.29 g of the compound (1) having an average value of n10 of 24 and 0.71 g of tetraethoxysilane were dissolved in 2.13 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0008 g of acetic acid as a catalyst and 0.14 g of water were dropped, and then stirred at room temperature for 4 hours to prepare a sample solution. The sample solution was diluted with 66.88 g of isopropyl acetate to obtain a coating solution 8. The coating solution 8 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
  • Example 9 The same as in Example 8 except that the mixing time for preparing the sample solution was 6 hours and the sample solution was diluted with a mixed solution of 29.68 g of isopanol and 37.05 g of 2-ethoxyethyl acetate to prepare the coating solution 9. Thus, a film was formed on the substrate.
  • Example 10 is the same as Example 8 except that the mixing time for preparing the sample solution was 6 hours and the sample solution was diluted with a mixed solution of 47.48 g of isopropanol and 14.82 g of 2-ethoxyethyl acetate to prepare the coating solution 10. Similarly, a film was formed on the substrate.
  • Example 11 In the above formula (AI-26), 0.43 g of compound (1) having an average value of n10 of 24 and 0.38 g of tetraethoxysilane were dissolved in 2.04 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0008 g of acetic acid as a catalyst and 0.14 g of water were dropped, and then stirred at room temperature for 4 hours to prepare a sample solution. The sample solution was diluted with 84.90 g of 2-ethoxyethyl acetate to obtain a coating solution 11. The coating solution 11 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
  • Example 12 A coating was formed on the substrate in the same manner as in Example 11, except that 84.39 g of 2-methoxy-1-methylethyl acetate was used instead of 84.90 g of 2-ethoxyethyl acetate. Formed.
  • Example 13 In the above formula (AI-26), 0.53 g of the compound (2) having an average value of n10 of 45 and 0.29 g of tetraethoxysilane were dissolved in 2.07 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0006 g of acetic acid as a catalyst and 0.10 g of water were dropped, and then stirred at room temperature for 4 hours to prepare a sample solution. The sample solution was diluted with 84.90 g of 2-ethoxyethyl acetate to obtain a coating solution 13. The coating solution 13 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
  • Example 14 A coating film was formed on the substrate in the same manner as in Example 13 except that 84.39 g of 2-methoxy-1-methylethyl acetate was used instead of 84.90 g of 2-ethoxyethyl acetate. Formed.
  • Example 15 In the above formula (AI-26), 0.28 g of the compound (2) having an average value of n10 of 45 and 0.54 g of tetraethoxysilane were dissolved in 2.01 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0011 g of acetic acid as a catalyst and 0.18 g of water were added dropwise, and then stirred at room temperature for 4 hours to prepare a sample solution. The sample solution was diluted with 84.90 g of 2-ethoxyethyl acetate to obtain a coating solution 15. The coating solution 15 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
  • Example 16 A coating was formed on the substrate in the same manner as in Example 15 except that 84.39 g of 2-methoxy-1-methylethyl acetate was used instead of 84.90 g of 2-ethoxyethyl acetate. Formed.
  • Comparative Example 1 In the above formula (AI-26), 0.29 g of the compound (1) having an average value of n10 of 24 and 0.71 g of tetraethoxysilane were dissolved in 2.13 g of isopropanol and stirred at room temperature for 20 minutes. After 0.17 g of acetic acid as a catalyst and 0.02 g of water were added dropwise to the obtained solution, the sample solution was stirred for 4 hours at room temperature. The sample solution was diluted with 71.44 g of 2-butoxyethyl acetate to obtain a coating solution a. The coating solution a was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
  • Comparative Example 2 A film was formed on the substrate in the same manner as in Comparative Example 1 except that the coating solution b was prepared by diluting the sample solution with 1-octanol 62.62 g.
  • Comparative Example 3 A film was formed on the substrate in the same manner as in Comparative Example 1 except that the coating solution c was prepared by diluting the sample solution with 59.36 g of isopropanol.
  • Table 6-1 The results are shown in Table 6-1, Table 6-2 and Table 7.
  • Table 8 shows the physical properties of the solvents used in Examples and Comparative Examples.
  • the film obtained from the mixed composition of the present invention is excellent in water repellency, abrasion resistance, sulfuric acid resistance and hot water resistance. Therefore, it is useful as a base material in display devices such as a touch panel display, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like. Furthermore, it is suitably used as an article such as a body, window glass (front glass, side glass, rear glass), mirror, bumper, etc. 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.

Abstract

The purpose of the present invention is to provide a composition that is capable of forming a film having excellent resistance to hot water.　The present invention pertains to a mixed composition of an organosilicon compound (a) in which at least one trialkylsilyl group–containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom, a metal compound (b) in which at least one hydrolyzable group is bonded to a metal atom, and a solvent (c2) in which the vapor pressure at 20°C is 0.032 kPa to 10 kPa and the sp value is no higher than 11 (cal/cm3)1/2, wherein the composition is characterized in that the hydrogen atoms included in the trialkylsilyl group may be substituted with fluorine atoms, the total amount of the organosilicon compound (a) and the metal compound (b) in the composition is at least 0.5 mass%, and the amount of the solvent (c2) in the composition is at least 5 mass%.

Description

混合組成物Mixed composition
　本発明は有機ケイ素化合物と金属化合物の混合組成物に関する。 The present invention relates to a mixed composition of an organosilicon compound and a metal compound.
　各種の表示装置、光学素子、半導体素子、建築材料、自動車部品、ナノインプリント技術等において、基材の表面に液滴が付着することにより、基材の汚れや腐食、さらにこの汚れや腐食に由来する性能低下等の問題が生じる場合がある。そのため、これらの分野において、基材表面の撥水性が良好であることが求められている。 In various display devices, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, etc., droplets adhere to the surface of the substrate, resulting in contamination and corrosion of the substrate, and further from this contamination and corrosion. Problems such as performance degradation may occur. Therefore, in these fields, it is required that the water repellency of the substrate surface is good.
　このような撥水性を有する組成物として、特許文献１には、炭素数が３～１８のアルキルアルコキシシラン等の有機シランと、金属アルコキシドを有機溶媒、水、触媒を含む溶液が開示され、該有機溶媒としては、蒸気圧が水より高いメタノール、エタノール、イソプロパノール、テトラヒドロフランなどが例示されている。また特許文献２には、有機ケイ素化合物と、金属化合物と、２０℃での蒸気圧が１０００Ｐａ以下であること及び沸点が１２０℃以上であることの少なくともいずれかを満たし、かつ溶解度パラメーターが８．０（ｃａｌ／ｃｍ3）1/2以上である高沸点溶媒（Ｃ）と、２０℃での蒸気圧が１０００Ｐａ超であり且つ沸点が１２０℃未満である低沸点溶媒（Ｄ）の混合組成物であって、前記高沸点溶媒（Ｃ）の濃度が、組成物１００質量部に対して、０．０８８質量部以上、１．７４質量部未満である混合組成物が開示されている。 As such a composition having water repellency, Patent Document 1 discloses a solution containing an organic silane such as an alkylalkoxysilane having 3 to 18 carbon atoms, a metal alkoxide, an organic solvent, water, and a catalyst. Examples of the organic solvent include methanol, ethanol, isopropanol, tetrahydrofuran and the like whose vapor pressure is higher than that of water. Further, Patent Document 2 satisfies at least one of an organosilicon compound, a metal compound, a vapor pressure at 20 ° C. of 1000 Pa or less, and a boiling point of 120 ° C. or more, and a solubility parameter of 8. A mixed composition of a high boiling point solvent (C) which is 0 (cal / cm 3 ) 1/2 or more and a low boiling point solvent (D) whose vapor pressure at 20 ° C. is more than 1000 Pa and whose boiling point is less than 120 ° C. And the mixed composition whose density | concentration of the said high boiling point solvent (C) is 0.088 mass part or more and less than 1.74 mass part with respect to 100 mass parts of compositions is disclosed.
ＷＯ２０１４／１３６２７５号WO2014 / 136275 特開２０１７－２０１００８号公報Japanese Patent Laid-Open No. 2017-201008
　ところで、撥水性の皮膜は、屋外などの用途によっては、紫外線や雨水などの過酷な環境に曝される場合があり、過酷な環境に曝された後にでも良好な性能を維持できることが好ましい。撥水性の皮膜に有機ケイ素化合物を用いた場合、光に対する安定性は非常に高いが、一方でシロキサン結合を有することから、水や温水に対する耐久性を持たせることが容易ではないことが分かってきた。そのため、有機ケイ素化合物を有する撥水性の皮膜において、過酷な環境に曝された後にでも良好な性能を維持させるためには、耐温水性の高い膜であることが、実使用環境においても性能を維持させるために重要な性能となると言える。 By the way, the water-repellent film may be exposed to harsh environments such as ultraviolet rays and rainwater depending on applications such as outdoors, and it is preferable that good performance can be maintained even after being exposed to harsh environments. When an organosilicon compound is used for a water-repellent film, the stability to light is very high. On the other hand, since it has a siloxane bond, it has been found that it is not easy to have durability against water and warm water. It was. Therefore, in order to maintain good performance even after being exposed to a harsh environment in a water-repellent film having an organosilicon compound, a film having a high temperature resistance to water can be used in an actual use environment. It can be said that this is an important performance to maintain.
　特許文献２では、有機ケイ素化合物として、トリアルキルシリル基含有分子鎖を有する有機ケイ素化合物が開示されており、有機ケイ素化合物と金属化合物の合計量は、組成物１００質量％に対して約０．３％程度であるが、皮膜の密着性等を考慮すると、有機ケイ素化合物と金属化合物の合計量をより高めることが望まれる。本発明者らの検討によれば、特許文献２の組成物において、有機ケイ素化合物と金属化合物の濃度を高めると、温水に対する耐久性（耐温水性）が悪化する傾向にあることが分かった。 Patent Document 2 discloses an organosilicon compound having a trialkylsilyl group-containing molecular chain as the organosilicon compound, and the total amount of the organosilicon compound and the metal compound is about 0. 0% with respect to 100% by mass of the composition. Although it is about 3%, it is desired to further increase the total amount of the organosilicon compound and the metal compound in consideration of the adhesion of the film. According to the study by the present inventors, it has been found that in the composition of Patent Document 2, when the concentrations of the organosilicon compound and the metal compound are increased, durability against warm water (warm water resistance) tends to deteriorate.
　そこで、本発明は、トリアルキルシリル基含有分子鎖を有する有機ケイ素化合物と金属化合物との合計濃度が高濃度である組成物であって、良好な耐温水性を有する皮膜を形成可能な組成物を提供することを目的とする。 Accordingly, the present invention provides a composition having a high total concentration of an organosilicon compound having a trialkylsilyl group-containing molecular chain and a metal compound, and capable of forming a film having good warm water resistance. The purpose is to provide.
　本発明者らが検討したところ、トリアルキルシリル基含有分子鎖を有する有機ケイ素化合物と金属化合物との合計濃度が０．５質量％以上である混合組成物では、所定の要件を満たす溶媒が混合されていることで、前記課題を達成できることを見出し、本発明を完成した。本発明は以下の通りである。 As a result of studies by the present inventors, in a mixed composition in which the total concentration of the organosilicon compound having a trialkylsilyl group-containing molecular chain and the metal compound is 0.5% by mass or more, a solvent that satisfies a predetermined requirement is mixed. As a result, the present inventors have found that the above-mentioned problems can be achieved and completed the present invention. The present invention is as follows.
［１］少なくとも１つのトリアルキルシリル基含有分子鎖と、少なくとも１つの加水分解性基とがケイ素原子に結合している有機ケイ素化合物（ａ）と、
　少なくとも１つの加水分解性基が金属原子に結合している金属化合物（ｂ）と、
　２０℃における蒸気圧が０．０３２ｋＰａ以上１０ｋＰａ以下、かつｓｐ値が１１（ｃａｌ／ｃｍ3）1/2以下である溶媒（ｃ２）の混合組成物であって、
　前記トリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
　組成物中の有機ケイ素化合物（ａ）及び金属化合物（ｂ）の合計量が０．５質量％以上であり、
　組成物中の前記溶媒（ｃ２）の量が５質量％以上であることを特徴とする混合組成物。 [1] an organosilicon compound (a) in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom;
A metal compound (b) having at least one hydrolyzable group bonded to a metal atom;
A mixed composition of a solvent (c2) having a vapor pressure at 20 ° C. of 0.032 kPa to 10 kPa and an sp value of 11 (cal / cm 3 ) 1/2 or less,
The hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom,
The total amount of the organosilicon compound (a) and the metal compound (b) in the composition is 0.5% by mass or more,
The mixed composition, wherein the amount of the solvent (c2) in the composition is 5% by mass or more.
［２］組成物中の前記溶媒（ｃ２）の量が３０質量％以上である［１］に記載の組成物。 [2] The composition according to [1], wherein the amount of the solvent (c2) in the composition is 30% by mass or more.
［３］２０℃における水の溶解度が２３１ｇ／Ｌ以上であり、かつｓｐ値が２０以下である溶媒（ｃ１）が混合されている［１］または［２］に記載の組成物。 [3] The composition according to [1] or [2], wherein a solvent (c1) having a water solubility at 20 ° C. of 231 g / L or more and an sp value of 20 or less is mixed.
［４］ｓｐ値が１１（ｃａｌ／ｃｍ3）1/2超である溶媒（ｃ１）が混合されている［１］または［２］に記載の組成物。 [4] The composition according to [1] or [2], wherein a solvent (c1) having an sp value of more than 11 (cal / cm 3 ) 1/2 is mixed.
［５］イソプロパノール、エタノール、メタノール及びメチルエチルケトンよりなる群から選択される溶媒（ｃ１）の少なくとも１種が混合されている［１］または［２］に記載の組成物。 [5] The composition according to [1] or [2], wherein at least one solvent (c1) selected from the group consisting of isopropanol, ethanol, methanol and methyl ethyl ketone is mixed.
［６］組成物中の水分量が０．５質量％以下である［１］～［５］のいずれかに記載の組成物。 [6] The composition according to any one of [1] to [5], wherein the water content in the composition is 0.5% by mass or less.
［７］前記有機ケイ素化合物（ａ）が、下記式（Ａ１）で表される化合物である［１］～［６］のいずれかに記載の組成物。
Figure JPOXMLDOC01-appb-C000004
 　［前記式（Ａ１）中、Ｒa1はトリアルキルシリル基含有分子鎖を表し、
　複数のＡa1は、それぞれ独立に、加水分解性基を表し、
　Ｚa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表し、
　Ｒa1及びＺa1におけるトリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく
　ｘは０または１である。］ [7] The composition according to any one of [1] to [6], wherein the organosilicon compound (a) is a compound represented by the following formula (A1).
Figure JPOXMLDOC01-appb-C000004
 [In the formula (A1), R a1 represents a trialkylsilyl group-containing molecular chain,
Several A <a1> represents a hydrolysable group each independently,
Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group,
A hydrogen atom contained in the trialkylsilyl group in R a1 and Z a1 may be substituted with a fluorine atom, and x is 0 or 1. ]
［８］前記金属化合物（ｂ）が下記式（Ｂ１）で表される化合物である［１］～［７］のいずれかに記載の組成物。
Figure JPOXMLDOC01-appb-C000005
［前記式（Ｂ１）中、ＭはＡｌ、Ｆｅ、Ｉｎ、Ｇｅ、Ｈｆ、Ｓｉ、Ｔｉ、Ｓｎ、Ｚｒ、または、Ｔａを表し、
　Ｚb1は、シロキサン骨格含有基、炭化水素鎖含有基又は水素原子を表し、
　複数のＡb1は、それぞれ独立に、加水分解性基を表し、
　ｍは、金属原子に応じて、３～５の整数を表し、
　ｒは０又は１である。］ [8] The composition according to any one of [1] to [7], wherein the metal compound (b) is a compound represented by the following formula (B1).
Figure JPOXMLDOC01-appb-C000005
[In the formula (B1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta,
Z b1 represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group or a hydrogen atom,
Several A <b1> represents a hydrolysable group each independently,
m represents an integer of 3 to 5, depending on the metal atom,
r is 0 or 1; ]
［９］前記有機ケイ素化合物（ａ）が下記式（Ａ２）で表される化合物である［１］～［８］のいずれかに記載の組成物。
Figure JPOXMLDOC01-appb-C000006
 ［前記式（Ａ２）中、
　複数のＡa1は、それぞれ独立に、加水分解性基を表し、
　Ｚa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表し、該トリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
　複数のＲs1は、それぞれ独立に、炭化水素基又はトリアルキルシリルオキシ基を表し、該炭化水素基又はトリアルキルシリルオキシ基に含まれる水素原子は、フッ素原子に置換されていてもよく、
　複数のＲs2は、それぞれ独立に、炭素数１～１０のアルキル基を表し、
　Ｚs1は、－Ｏ－又は２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。
　Ｙs1は単結合又は－Ｓｉ（Ｒs2）2－Ｌs1－を表し、該Ｌs1は、２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。
　ｎ１は、１以上の整数を表し、
　ｘは０または１である。］ [9] The composition according to any one of [1] to [8], wherein the organosilicon compound (a) is a compound represented by the following formula (A2).
Figure JPOXMLDOC01-appb-C000006
 [In the formula (A2),
Several A <a1> represents a hydrolysable group each independently,
Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group, and a hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom,
A plurality of R s1 each independently represents a hydrocarbon group or a trialkylsilyloxy group, and a hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group may be substituted with a fluorine atom,
A plurality of R s2 each independently represents an alkyl group having 1 to 10 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 —, the L s1 represents a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group is -O- may be substituted.
n1 represents an integer of 1 or more,
x is 0 or 1. ]
　本発明の混合組成物によれば、得られる皮膜の、温水試験後の滑落速度で評価される耐温水特性が良好である。 According to the mixed composition of the present invention, the obtained film has good hot water resistance as evaluated by the sliding speed after the hot water test.
　本発明の組成物は、有機ケイ素化合物（ａ）及び金属化合物（ｂ）が合計量で０．５質量％以上であると共に、所定の要件を満たす溶媒（ｃ２）が混合されているため、得られる皮膜の耐温水性が良好であり、好ましくは皮膜の透明性を良好にすることもできる。以下、有機ケイ素化合物（ａ）、金属化合物（ｂ）、溶媒（ｃ２）について順に説明する。なお、前記混合組成物は、混合後、例えば保管中に反応が進んだものも含む。 The composition of the present invention is obtained because the organosilicon compound (a) and the metal compound (b) are not less than 0.5% by mass in total and the solvent (c2) satisfying the predetermined requirements is mixed. The resulting film has good hot water resistance, and preferably the film can have good transparency. Hereinafter, the organosilicon compound (a), the metal compound (b), and the solvent (c2) will be described in order. In addition, the said mixed composition contains the thing which reaction advanced, for example during storage after mixing.
　１．有機ケイ素化合物（ａ）
　本発明における有機ケイ素化合物（ａ）は、少なくとも１つのトリアルキルシリル基含有分子鎖と、少なくとも１つの加水分解性基とがケイ素原子（以下、このケイ素原子を「中心ケイ素原子」という場合がある）に結合している。 1. Organosilicon compound (a)
In the organosilicon compound (a) in the present invention, at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group may be referred to as a silicon atom (hereinafter, this silicon atom may be referred to as “central silicon atom”). ).
　トリアルキルシリル基含有分子鎖とは、トリアルキルシリル含有基が分子鎖の末端に結合した構造を有する１価の基であり、分子鎖にトリアルキルシリル含有基が結合していることで、本発明の混合組成物から形成される皮膜の撥水性が向上する。またトリアルキルシリル基含有分子鎖が存在することで、液滴（水滴等）と該皮膜の間の抵抗が低減され、液滴が移動しやすくなる。トリアルキルシリル含有基のアルキル基がフルオロアルキル基に置き換わっている場合においても、同様に該皮膜界面（表面）の撥水性を向上することができる。 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 of the film formed from the mixed composition of the invention is improved. Further, the presence of the trialkylsilyl group-containing molecular chain reduces the resistance between the droplet (water droplet or the like) and the film, and the droplet easily moves. Even when the alkyl group of the trialkylsilyl-containing group is replaced with a fluoroalkyl group, the water repellency at the film interface (surface) can be improved in the same manner.
　有機ケイ素化合物（ａ）において、中心ケイ素原子に結合するトリアルキルシリル基含有分子鎖の個数は、１以上であり、３以下であることが好ましく、より好ましくは２以下であり、特に好ましくは１である。 In the organosilicon compound (a), the number of trialkylsilyl group-containing molecular chains bonded to the central silicon atom is 1 or more, preferably 3 or less, more preferably 2 or less, and particularly preferably 1 It is.
　前記加水分解性基としては、加水分解により、ヒドロキシ基を与える（ケイ素原子と結合してシラノール基となる）基であればよく、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；アセトキシ基；塩素原子；イソシアネート基；等を好ましく挙げることができる。中でも、炭素数１～６のアルコキシ基であることが好ましく、炭素数１～４のアルコキシ基であることがより好ましく、炭素数１～２のアルコキシ基であることがさらに好ましい。
　有機ケイ素化合物（ａ）において、中心ケイ素原子に結合する加水分解性基の個数は、１以上であり、２以上であることが好ましく、通常、３以下であることが好ましい。 The hydrolyzable group may be a group that gives a hydroxy group by hydrolysis (to form a silanol group by bonding with a silicon atom), and examples thereof include carbon such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Preferred examples include an alkoxy group of 1 to 6; a hydroxy group; an acetoxy group; a chlorine atom; an isocyanate group; Among these, an alkoxy group having 1 to 6 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is further preferable.
In the organosilicon compound (a), the number of hydrolyzable groups bonded to the central silicon atom is 1 or more, preferably 2 or more, and usually 3 or less.
　有機ケイ素化合物（ａ）の中心ケイ素原子には、トリアルキルシリル基含有分子鎖、加水分解性基のほか、シロキサン骨格含有基（好ましくはトリアルキルシリル基含有分子鎖の分子鎖を構成する元素数よりも少ない元素数のシロキサン骨格含有基）、又は炭化水素鎖含有基（好ましくはトリアルキルシリル基含有分子鎖の分子鎖を構成する元素数よりも少ない炭素数の炭化水素鎖を含有する炭化水素鎖含有基）が結合していてもよい。 In addition to the trialkylsilyl group-containing molecular chain and hydrolyzable group, the central silicon atom of the organosilicon compound (a) includes a siloxane skeleton-containing group (preferably the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain) A siloxane skeleton-containing group having a smaller number of elements), or a hydrocarbon chain-containing group (preferably a hydrocarbon chain having a hydrocarbon chain having fewer carbon atoms than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain) A chain-containing group) may be bonded.
　前記有機ケイ素化合物（ａ）は、具体的には、下記式（Ａ１）で表される化合物であることが好ましい。 Specifically, the organosilicon compound (a) is preferably a compound represented by the following formula (A1).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　［前記式（Ａ１）中、Ｒa1はトリアルキルシリル基含有分子鎖を表し、複数のＡa1は、それぞれ独立に、加水分解性基を表し、Ｚa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表し、Ｒa1及びＺa1におけるトリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、ｘは０または１である。］ [In the formula (A1), R a1 represents a trialkylsilyl group-containing molecular chain, a plurality of A a1 each independently represents a hydrolyzable group, Z a1 represents a trialkylsilyl group-containing molecular chain, It represents a siloxane skeleton-containing group or a hydrocarbon chain-containing group, the hydrogen atom contained in the trialkylsilyl group in R a1 and Z a1 may be substituted with a fluorine atom, and x is 0 or 1. ]
　Ｒa1は、トリアルキルシリル基含有分子鎖であり、上述した通りトリアルキルシリル含有基が分子鎖の末端に結合した構造を有する１価の基である。 R a1 is a trialkylsilyl group-containing molecular chain and is a monovalent group having a structure in which a trialkylsilyl-containing group is bonded to the end of the molecular chain as described above.
　前記トリアルキルシリル含有基は、少なくとも１つのトリアルキルシリル基を含む基であり、好ましくは２つ以上、さらに好ましくは３つのトリアルキルシリル基を含む。トリアルキルシリル含有基は、式（ｓ１）で表される基であることが好ましい。 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).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式（ｓ１）中、複数のＲs1は、それぞれ独立に、炭化水素基又はトリアルキルシリルオキシ基を表し、該炭化水素基又はトリアルキルシリルオキシ基に含まれる水素原子は、フッ素原子に置換されていてもよい。＊は結合手を表す。上記式（ｓ１）において、Ｒs1の少なくとも１つがトリアルキルシリルオキシ基であるか、Ｒs1が全てアルキル基であることが好ましい。 In formula (s1), each of the plurality of R s1 independently represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group is substituted with a fluorine atom. It may be. * Represents a bond. In the above formula (s1), or that at least one trialkyl silyl group of R s1, it is preferred that R s1 are all alkyl groups.
　Ｒs1が炭化水素基である場合、その炭素数は、１～４であることが好ましく、より好ましくは１～３、さらに好ましくは１～２である。Ｒs1が炭化水素基である場合、脂肪族炭化水素基が好ましく、アルキル基がより好ましい。該アルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられる。複数のＲs1は、同一でも異なっていてもよく、同一であることが好ましい。Ｒs1が全て炭化水素基である場合（特にアルキル基）、３つのＲs1の合計の炭素数は、９以下であることが好ましく、より好ましくは６以下、さらに好ましくは４以下である。３つのＲs1のうち少なくとも１つがメチル基であることが好ましく、少なくとも２つがメチル基であることがより好ましく、３つのＲs1全てがメチル基であることが特に好ましい。 When R s1 is a hydrocarbon group, the carbon number thereof is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. When R s1 is a hydrocarbon group, an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. 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. When all of R s1 are hydrocarbon groups (particularly alkyl groups), the total number of carbon atoms of the three R s1 is preferably 9 or less, more preferably 6 or less, and even more preferably 4 or less. 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.
　Ｒs1が全て炭化水素基（アルキル基）である基（トリアルキルシリル基）としては、具体的には、下記式で表される基等が挙げられる。式中、＊は結合手を表す。 Specific examples of the group (trialkylsilyl group) in which R s1 is a hydrocarbon group (alkyl group) include groups represented by the following formulas. In the formula, * represents a bond.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　上記式（ｓ１）において、Ｒs1の少なくとも１つが、トリアルキルシリルオキシ基であることが好ましい。前記トリアルキルシリルオキシ基としては、Ｒs1が全て炭化水素基（アルキル基）である基（トリアルキルシリル基）のケイ素原子に酸素原子が結合している基が挙げられる。上記式（ｓ１）において、２個以上のＲs1がトリアルキルシリルオキシ基であることが好ましく、３個のＲs1がトリアルキルシリルオキシ基であることが更に好ましい。 In the above formula (s1), it is preferable that at least one of R s1 is a trialkylsilyloxy group. Examples of 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). In the above formula (s1), two or more R s1 are preferably a trialkylsilyloxy group, and more preferably three R s1 are a trialkylsilyloxy group.
　Ｒs1の少なくとも１つがトリアルキルシリルオキシ基である基としては、下記式で表される基が挙げられる。 Examples of the group in which at least one of R s1 is a trialkylsilyloxy group include groups represented by the following formulae.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　トリアルキルシリル基含有分子鎖において、トリアルキルシリル含有基は、分子鎖の末端（自由端側）、特に分子鎖の主鎖（最長直鎖）の末端（自由端側）に結合していることが好ましい。 In a trialkylsilyl group-containing molecular chain, the trialkylsilyl-containing group must be bonded to the end (free end side) of the molecular chain, particularly the end of the main chain (longest straight chain) (free end side). Is preferred.
　トリアルキルシリル含有基が結合している分子鎖は、直鎖状又は分岐鎖状であることが好ましく、直鎖状であることが好ましい。前記分子鎖は、ジアルキルシロキサン鎖を含むことが好ましく、直鎖状ジアルキルシロキサン鎖を含むことが好ましい。またジアルキルシロキサン鎖を含む前記分子鎖は、２価の炭化水素基を含んでいてもよい。分子鎖の一部が２価の炭化水素基であっても、残部がジアルキルシロキサン鎖であるため、得られる皮膜の化学的・物理的耐久性が良好である。 The molecular chain to which the trialkylsilyl-containing 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 containing a dialkylsiloxane 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.
　前記分子鎖は、式（ｓ２）で表される基であることが好ましい。 The molecular chain is preferably a group represented by the formula (s2).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　式（ｓ２）中、複数のＲs2は、それぞれ独立に、炭素数１～１０のアルキル基を表す。Ｚs1は、－Ｏ－又は２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。Ｙs1は、単結合又は－Ｓｉ（Ｒs2）2－Ｌs1－を表す。Ｌs1は、２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。左側の＊は、中心ケイ素原子との結合手を表し、右側の＊はトリアルキルシリル含有基との結合手を表す。 In the formula (s2), a plurality of R s2 each independently represents an alkyl group having 1 to 10 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.
　Ｒs2の炭素数は、１～４であることが好ましく、より好ましくは１～３、さらに好ましくは１～２である。 R s2 preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and still more preferably 1 to 2.
　ｎ１は、１～１００であることが好ましく、より好ましくは１～８０、さらに好ましくは１～６０、ことさらに好ましくは１～４５、特に好ましくは１～３０である。 N1 is preferably 1 to 100, more preferably 1 to 80, still more preferably 1 to 60, still more preferably 1 to 45, and particularly preferably 1 to 30.
　Ｚs1又はＬs1で表される２価の炭化水素基の炭素数は、１～１０であることが好ましく、より好ましくは１～６、さらに好ましくは１～４である。前記２価の炭化水素基は、鎖状であることが好ましく、鎖状である場合、直鎖状、分岐鎖状のいずれであってもよい。また、前記２価の炭化水素基は、２価の脂肪族炭化水素基であることが好ましく、アルカンジイル基であることが好ましい。２価の炭化水素基としては、メチレン基、エチレン基、プロピレン基、ブチレン基等が挙げられる。 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.
　さらに、前記２価の炭化水素基に含まれる一部の－ＣＨ2－は－Ｏ－に置き換わっていてもよい。この場合連続する２つの－ＣＨ2－が同時に－Ｏ－に置き換わることはなく、Ｓｉ原子に隣接する－ＣＨ2－が－Ｏ－に置き換わることはない。２つ以上の－ＣＨ2－が－Ｏ－に置き換わっている場合、－Ｏ－と－Ｏ－の間の炭素原子数は、２～４であることが好ましく、２～３であることがさらに好ましい。２価の炭化水素基の一部が－Ｏ－に置き換わった基としては、具体的には、（ポリ）エチレングリコール単位を有する基、（ポリ）プロピレングリコール単位を有する基等を例示することができる。 Furthermore, a part of —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—. In this case, two consecutive —CH 2 — are not simultaneously replaced with —O—, and —CH 2 — adjacent to the Si atom is not replaced with —O—. When two or more —CH 2 — are replaced by —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.
　前記式（ｓ２）において、Ｚs1が－Ｏ－であり、Ｙs1が単結合であること、すなわち前記分子鎖は、ジアルキルシリルオキシ基の繰り返しのみからなることが好ましい。ジアルキルシロキサン鎖がジアルキルシリルオキシ基の繰り返しのみからなる場合、得られる皮膜の化学的・物理的耐久性が良好である。 In the formula (s2), it is preferable that Z s1 is —O— and Y s1 is a single bond, that is, the molecular chain is composed only of repeating dialkylsilyloxy groups. When the dialkylsiloxane chain consists only of repeating dialkylsilyloxy groups, the resulting film has good chemical and physical durability.
　トリアルキルシリル基含有分子鎖に含まれる分子鎖としては、下記式で表される分子鎖を挙げることができる。式中、ｑ１は１～６０の整数を表し、＊は、中心ケイ素原子又はトリアルキルシリル含有基に結合する結合手を表すものとする。ｑ１は、上記ｎ１と同じ数値範囲であることができ、好ましくは１～３０の整数である。 Examples of the molecular chain contained in the trialkylsilyl group-containing molecular chain include a molecular chain represented by the following formula. In the formula, q1 represents an integer of 1 to 60, and * represents a bond bonded to a central silicon atom or a trialkylsilyl-containing group. q1 can be in the same numerical range as n1, and is preferably an integer of 1 to 30.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　また、トリアルキルシリル基含有分子鎖を構成する元素の合計数は、２４以上であることが好ましく、より好ましくは４０以上、さらに好ましくは５０以上である。また、好ましくは５０００以下であり、より好ましくは４０００以下、さらに好ましくは２０００以下、ことさら好ましくは１２００以下、より一層好ましくは７００以下、特に好ましく２５０以下である。 In addition, the total number of elements constituting the trialkylsilyl group-containing molecular chain is preferably 24 or more, more preferably 40 or more, and still more preferably 50 or more. Further, it is preferably 5000 or less, more preferably 4000 or less, still more preferably 2000 or less, even more preferably 1200 or less, still more preferably 700 or less, and particularly preferably 250 or less.
　トリアルキルシリル基含有分子鎖は、下記式（ｓ３）で表される基であることが好ましい。 The trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s3).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　前記式（ｓ３）中、Ｒs1、Ｒs2、Ｚs1、Ｙs1、ｎ１は、上記と同義である。＊は、中心ケイ素原子との結合手を表す。 In the formula (s3), R s1 , R s2 , Z s1 , Y s1 , and n1 are as defined above. * Represents a bond with the central silicon atom.
　トリアルキルシリル基含有分子鎖は、下記式（ｓ３－１）又は下記式（ｓ３－２）で表される基であることが好ましく、下記式（ｓ３－２）で表される基であることがより好ましい。 The trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s3-1) or (s3-2), and preferably a group represented by the following formula (s3-2). Is more preferable.
　トリアルキルシリル基含有分子鎖が、下記式（ｓ３－１）で表される場合、下記式（ｓ３－１－１）で表される基であることがより好ましい。 When the trialkylsilyl group-containing molecular chain is represented by the following formula (s3-1), it is more preferably a group represented by the following formula (s3-1-1).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式（ｓ３－１）及び式（ｓ３－１－１）中、Ｒs2、Ｙs1、Ｚs1、ｎ１は上記と同義である。Ｒs3は、炭素数１～４のアルキル基を表す。＊は、中心ケイ素原子との結合手を表す。 In formula (s3-1) and formula (s3-1-1), R s2 , Y s1 , Z s1 , and n1 have the same meanings as described above. R s3 represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond with the central silicon atom.
　Ｒs3で表されるアルキル基の炭素数は１～３であることが好ましく、より好ましくは１～２である。また、式（ｓ３－１）及び式（３－１－１）中、＊－Ｓｉ（Ｒs3）3に含まれるＲs3の合計の炭素数は、９以下であることが好ましく、より好ましくは６以下、さらに好ましくは４以下である。さらに、＊－Ｓｉ（Ｒs3）3に含まれるＲs3のうち、少なくとも１つがメチル基であることが好ましく、２つ以上のＲs3がメチル基であることが好ましく、３つのＲs3全てがメチル基であることが特に好ましい。 The number of carbon atoms of the alkyl group represented by R s3 is preferably 1 to 3, more preferably 1 to 2. In the formulas (s3-1) and (3-1-1), the total carbon number of R s3 contained in * -Si (R s3 ) 3 is preferably 9 or less, more preferably 6 or less, 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.
　また、トリアルキルシリル基含有分子鎖が、下記式（ｓ３－２）で表される場合、下記式（ｓ３－２－１）で表される基であることがより好ましい。 Further, when the trialkylsilyl group-containing molecular chain is represented by the following formula (s3-2), it is more preferably a group represented by the following formula (s3-2-1).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式（ｓ３－２）及び（ｓ３－２－１）中、Ｒs2、Ｙs1、Ｚs1、ｎ１は上記と同義である。Ｒs4は、炭素数１～４のアルキル基を表す。＊は中心ケイ素原子との結合手を表す。 In the formulas (s3-2) and (s3-2-1), R s2 , Y s1 , Z s1 , and n1 have the same meanings as described above. R s4 represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond with the central silicon atom.
　トリアルキルシリル基含有分子鎖としては式（ｓ３－Ｉ）で表される基が挙げられる。式（ｓ３－Ｉ）中、＊は中心ケイ素原子との結合手を表す。 Examples of the trialkylsilyl group-containing molecular chain include a group represented by the formula (s3-I). In the formula (s3-I), * represents a bond with the central silicon atom.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
　上記式（ａ１）中、ｎ１０は１～３０であることが好ましい。 In the above formula (a1), n10 is preferably 1 to 30.
　次に、式（Ａ１）におけるＡa1について説明する。複数のＡa1は、それぞれ独立に、加水分解性基であり、加水分解によりヒドロキシ基（シラノール基）を与える基であればよく、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１～４のアルコキシ基；ヒドロキシ基；アセトキシ基；塩素原子；イソシアネート基；等を好ましく挙げることができる。中でも、炭素数１～４のアルコキシ基が好ましく、炭素数１～２のアルコキシ基がより好ましい。 Next, A a1 in the formula (A1) will be described. A plurality of A a1 are each independently a hydrolyzable group and may be any group that gives a hydroxy group (silanol group) by hydrolysis. For example, carbon such as methoxy group, ethoxy group, propoxy group, butoxy group, etc. Preferred examples include an alkoxy group having 1 to 4; a hydroxy group; an acetoxy group; a chlorine atom; an isocyanate group; 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.
　式（Ａ１）におけるＺa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表す。Ｚa1がトリアルキルシリル基含有分子鎖である場合は、上記Ｒa1と同様のものが挙げられる。 Z a1 in the formula (A1) represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group. When Z a1 is a trialkylsilyl group-containing molecular chain, the same as the above R a1 can be mentioned.
　また、Ｚa1がシロキサン骨格含有基である場合、前記シロキサン骨格含有基は、シロキサン単位（Ｓｉ－Ｏ－）を含有する１価の基であり、Ｒa1のトリアルキルシリル基含有分子鎖を構成する元素数よりも少ない数の元素で構成されるものであることが好ましい。これにより、シロキサン骨格含有基は、トリアルキルシリル基含有分子鎖よりも長さが短いか、立体的な広がり（かさ高さ）が小さな基となる。シロキサン骨格含有基には、２価の炭化水素基が含まれていてもよい。 In the case where Z a1 is a siloxane skeleton-containing group, the siloxane skeleton-containing group is a monovalent group containing a siloxane unit (Si—O—), and constitutes a trialkylsilyl group-containing molecular chain of R a1. It is preferable that the number of elements is smaller than the number of elements to be formed. As a result, 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.
　シロキサン骨格含有基は、下記式（ｓ４）で表される基であることが好ましい。 The siloxane skeleton-containing group is preferably a group represented by the following formula (s4).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　式（ｓ４）中、Ｒs2、Ｚs1、及びＹs1は上記と同義である。Ｒs5は、炭化水素基又はヒドロキシ基を表し、該炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよく、該炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。ｎ３は、０～５の整数を表す。＊は、中心ケイ素原子との結合手を表す。 In formula (s4), R s2 , Z s1 , and Y s1 have the same meanings 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. n3 represents an integer of 0 to 5. * Represents a bond with the central silicon atom.
　Ｒs5で表される炭化水素基としては、Ｒs1で表される炭化水素基と同様の基が挙げられ、脂肪族炭化水素基が好ましく、アルキル基がより好ましい。炭素数は１～４であることが好ましく、より好ましくは１～３、さらに好ましくは１～２である。 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.
　ｎ３は、１～５であることが好ましく、より好ましくは１～３である。 N3 is preferably 1 to 5, and more preferably 1 to 3.
　シロキサン骨格含有基の元素数の合計は、６００以下が好ましく、より好ましくは５００以下、さらに好ましくは３５０以下、ことさらに好ましくは１００以下、より一層好ましくは５０以下、特に好ましくは３０以下であり、また１０以上であることが好ましい。また、Ｒa1のトリアルキルシリル基含有分子鎖とＺa1のシロキサン骨格含有基の元素数の差は、１０以上であることが好ましく、より好ましくは２０以上であり、１０００以下であることが好ましく、より好ましくは５００以下、さらに好ましくは２００以下である。 The total number of elements of the siloxane skeleton-containing group is preferably 600 or less, more preferably 500 or less, further preferably 350 or less, still more preferably 100 or less, still more preferably 50 or less, and particularly preferably 30 or less. Moreover, it is preferable that it is 10 or more. The difference in the number of elements between the molecular chain containing R a1 trialkylsilyl group and the group containing Z a1 siloxane skeleton is preferably 10 or more, more preferably 20 or more, and preferably 1000 or less. More preferably, it is 500 or less, More preferably, it is 200 or less.
　シロキサン骨格含有基としては、具体的には、下記式で表される基が挙げられる。 Specific examples of the siloxane skeleton-containing group include groups represented by the following formulas.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　Ｚa1が炭化水素鎖含有基である場合、トリアルキルシリル基含有分子鎖の分子鎖を構成する元素数よりも炭化水素鎖部分の炭素数が少ないものであることが好ましい。また、トリアルキルシリル基含有分子鎖の最長直鎖を構成する元素数よりも、炭化水素鎖の最長直鎖の炭素数が少ないものであることが好ましい。炭化水素鎖含有基は、通常、炭化水素基（炭化水素鎖）のみから構成されるが、必要により、この炭化水素鎖の一部のメチレン基（－ＣＨ2－）が酸素原子に置き換わった基であってもよい。また、Ｓｉ原子に隣接するメチレン基（－ＣＨ2－）は酸素原子に置き換わることはなく、また連続する２つのメチレン基（－ＣＨ2－）が同時に酸素原子に置き換わることもない。 When Za1 is a hydrocarbon chain-containing group, it is preferable that the hydrocarbon chain portion has a smaller number of carbon atoms than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain. The number of carbon atoms of the longest straight chain of the hydrocarbon chain is preferably smaller than the number of elements constituting the longest straight chain of the trialkylsilyl group-containing molecular chain. The hydrocarbon chain-containing group is usually composed only of a hydrocarbon group (hydrocarbon chain), but if necessary, a group in which a part of the methylene group (—CH 2 —) of the hydrocarbon chain is replaced with an oxygen atom. It may be. 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.
　なお、炭化水素鎖部分の炭素数とは、酸素非置換型の炭化水素鎖含有基では炭化水素基（炭化水素鎖）を構成する炭素原子の数を意味し、酸素置換型の炭化水素鎖含有基では、酸素原子をメチレン基（－ＣＨ2－）と仮定して数えた炭素原子の数を意味するものとする。 In addition, 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, the number of carbon atoms is assumed assuming that the oxygen atom is a methylene group (—CH 2 —).
　以下、特に断りがない限り、酸素非置換型の炭化水素鎖含有基（すなわち１価の炭化水素基）を例にとって炭化水素鎖含有基について説明するが、いずれの説明でも、そのメチレン基（－ＣＨ2－）のうち一部を酸素原子に置き換えることが可能である。 Hereinafter, unless otherwise specified, the 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, the methylene group (— Part of CH 2 —) can be replaced with oxygen atoms.
　前記炭化水素鎖含有基は、それが炭化水素基の場合には、炭素数は１以上、３以下であることが好ましく、より好ましくは１である。また、前記炭化水素鎖含有基は、分岐鎖であっても直鎖であってもよい。前記炭化水素鎖含有基は、飽和又は不飽和の脂肪族炭化水素鎖含有基であることが好ましく、飽和脂肪族炭化水素鎖含有基であることがより好ましい。前記飽和脂肪族炭化水素鎖含有基としては、飽和脂肪族炭化水素基がより好ましい。飽和脂肪族炭化水素基には、例えば、メチル基、エチル基、プロピル基等が含まれる。 When the hydrocarbon chain-containing group is a hydrocarbon group, the number of carbon atoms is preferably 1 or more and 3 or less, more preferably 1. Further, the hydrocarbon chain-containing group may be branched or linear. The hydrocarbon chain-containing 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 more preferably a saturated aliphatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, and a propyl group.
　飽和脂肪族炭化水素基の一部のメチレン基（－ＣＨ2－）が酸素原子に置き換わる場合、具体的には、（ポリ）エチレングリコール単位を有する基等を例示することができる。 When a partial methylene group (—CH 2 —) of a saturated aliphatic hydrocarbon group is replaced with an oxygen atom, specific examples include a group having a (poly) ethylene glycol unit.
　式（Ａ１）におけるｘは０または１であり、好ましくは０である。 X in the formula (A1) is 0 or 1, preferably 0.
　Ａa1で表される加水分解性基は、上述の有機ケイ素化合物（ａ）が有する加水分解性基として説明した通り、加水分解により、ヒドロキシ基を与える（ケイ素原子と結合してシラノール基となる）基であり、上記で例示したものが採用できる。 The hydrolyzable group represented by A a1 gives a hydroxy group by hydrolysis as described above as the hydrolyzable group possessed by the organosilicon compound (a) (bonded to a silicon atom to form a silanol group). ) Group, and those exemplified above can be employed.
　式（Ａ１）で表される有機ケイ素化合物（ａ）は、下記式（Ａ２）で表される化合物であることが好ましい。 The organosilicon compound (a) represented by the formula (A1) is preferably a compound represented by the following formula (A2).
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　上記式（Ａ２）中、Ｒs1、Ｒs2、Ｚs1、Ｙs1、ｎ１、Ａa1、Ｚa1、ｘは、それぞれ上記と同義である。 In the above formula (A2), R s1 , R s2 , Z s1 , Y s1 , n1, A a1 , Z a1 , and x are as defined above.
　上記式（Ａ２）で表される有機ケイ素化合物（ａ）は、下記式（Ａ２－１）又は下記式（Ａ２－２）で表されることが好ましく、下記式（Ａ２－２）で表されることがより好ましい。 The organosilicon compound (a) represented by the above formula (A2) is preferably represented by the following formula (A2-1) or the following formula (A2-2), and is represented by the following formula (A2-2). More preferably.
　上記式（Ａ２）で表される有機ケイ素化合物（ａ）が、下記式（Ａ２－１）で表される場合、式（Ａ２－１－１）で表される化合物であることがより好ましい。 When the organosilicon compound (a) represented by the above formula (A2) is represented by the following formula (A2-1), it is more preferably a compound represented by the formula (A2-1-1).
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　上記式（Ａ２－１）及び上記式（Ａ２－１－１）中、Ｒs2、Ｒs3、Ｙs1、Ｚs1、ｎ１、Ａa1は上記と同義である。 In the above formula (A2-1) and the above formula (A2-1-1), R s2 , R s3 , Y s1 , Z s1 , n1 and A a1 are as defined above.
　上記式（Ａ２）で表される有機ケイ素化合物（ａ）が、下記式（Ａ２－２）で表される化合物である場合、下記式（Ａ２－２－１）で表される化合物であることがより好ましい。 When the organosilicon compound (a) represented by the above formula (A2) is a compound represented by the following formula (A2-2), it is a compound represented by the following formula (A2-2-1) Is more preferable.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　上記式（Ａ２－２）及び上記式（Ａ２－２－１）中、Ｒs2、Ｒs4、Ｙs1、Ｚs1、ｎ１、Ａa1は上記と同義である。 In the above formula (A2-2) and the above formula (A2-2-1), R s2 , R s4 , Y s1 , Z s1 , n1 and A a1 are as defined above.
　上記式（Ａ２）で表される有機ケイ素化合物（ａ）としては、具体的には、式（Ａ－Ｉ）で表される化合物が挙げられる。 Specific examples of the organosilicon compound (a) represented by the above formula (A2) include compounds represented by the formula (AI).
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　上記表３－１の（Ａ－Ｉ－１）～（Ａ－Ｉ－２５）におけるｎ１０は、いずれも１～３０であることが好ましい。 N10 in (AI-1) to (AI-25) in Table 3-1 are all preferably 1 to 30.
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　上記表３－２の（Ａ－Ｉ－２６）～（Ａ－Ｉ－５０）におけるｎ１０は、いずれも１～３０であることが好ましい。 N10 in (AI-26) to (AI-50) in Table 3-2 are all preferably 1 to 30.
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
　上記表４－１及び表４－２中、（Ａ－Ｉ－５１）～（Ａ－Ｉ－１００）におけるｎ１０は、いずれも１～３０であることが好ましい。 In Tables 4-1 and 4-2, each of n10 in (AI-51) to (AI-100) is preferably 1 to 30.
　上記（Ａ－Ｉ）式の中でも、（Ａ－Ｉ－２６）で表されるものがより好ましい。すなわち、式（Ａ２）で表される有機ケイ素化合物（ａ）としては、下記式で表される化合物が好ましい。 Among the above formulas (AI), those represented by (AI-26) are more preferable. That is, the organosilicon compound (a) represented by the formula (A2) is preferably a compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　上記式（Ａ－Ｉ－２６）中、ｎ１０は１～６０であり、好ましくは１～５０であり、より好ましくは１～３０である。 In the above formula (AI-26), n10 is 1 to 60, preferably 1 to 50, more preferably 1 to 30.
　上記有機ケイ素化合物（ａ）の合成方法の例としては、特開２０１７－２０１００９号公報記載の方法が挙げられる。 Examples of the method for synthesizing the organosilicon compound (a) include a method described in JP-A-2017-201109.
　有機ケイ素化合物（ａ）の量は、組成物１００質量％中、例えば０．２質量％以上であり、より好ましくは０．３質量％以上であり、また３．０質量％以下が好ましく、より好ましくは２．０質量％以下である。上記の有機ケイ素化合物（ａ）の量は、組成物の調製時の配合量及び組成物の分析結果から算出した値のいずれかが、上記範囲を満たすことが好ましい。なお、本明細書において、各成分の量、質量比またはモル比の範囲を記載している場合、上記と同様に、組成物の調製時の配合量及び組成物の分析結果から算出した値のいずれかが、該範囲を満たすことが好ましい。 The amount of the organosilicon compound (a) is, for example, 0.2% by mass or more, more preferably 0.3% by mass or more, and preferably 3.0% by mass or less, in 100% by mass of the composition. Preferably it is 2.0 mass% or less. As for the amount of the above-mentioned organosilicon compound (a), it is preferable that either the blending amount at the time of preparing the composition or the value calculated from the analysis result of the composition satisfies the above range. In addition, in this specification, when describing the amount, mass ratio, or molar ratio range of each component, the value calculated from the blending amount at the time of preparation of the composition and the analysis result of the composition is the same as above. It is preferable that either satisfies the range.
　本発明の混合組成物は、２種以上の有機ケイ素化合物（ａ）を用いてもよい。また、有機ケイ素化合物（ａ）は、組成物中において、縮合物となっていてもよい。 The mixed composition of the present invention may use two or more organic silicon compounds (a). The organosilicon compound (a) may be a condensate in the composition.
　２．金属化合物（ｂ）
　金属化合物（ｂ）は、少なくとも１つの加水分解性基が金属原子（以下、金属原子Ｍという場合がある）に結合している化合物である。金属化合物（ｂ）の金属原子Ｍとしては、アルコキシ基と結合して金属アルコキシドを形成しうる金属原子であればよく、本明細書における金属原子は、Ｓｉ、Ｇｅ等の半金属も含む意味で用いる。具体的には、Ａｌ、Ｆｅ、Ｉｎ等の３価金属；Ｇｅ、Ｈｆ、Ｓｉ、Ｔｉ、Ｓｎ、Ｚｒ等の４価金属、Ｔａ等の５価金属等が挙げられ、３価金属又は４価金属が好ましい。より好ましくは、Ａｌ等の３価金属又はＳｉ、Ｔｉ、Ｚｒ、Ｓｎ等の４価金属であり、更に好ましくはＡｌ、Ｓｉ、Ｔｉ、Ｚｒであり、最も好ましくはＳｉである。 2. Metal compound (b)
The metal compound (b) is a compound in which at least one hydrolyzable group is bonded to a metal atom (hereinafter sometimes referred to as a metal atom M). The metal atom M of the metal compound (b) may be any metal atom that can be bonded to an alkoxy group to form a metal alkoxide, and the metal atom in this specification includes a semimetal such as Si or Ge. Use. Specific examples 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. Metal is preferred. More preferred are trivalent metals such as Al or tetravalent metals such as Si, Ti, Zr and Sn, still more preferred are Al, Si, Ti and Zr, and most preferred is Si.
　金属化合物（ｂ）の加水分解性基としては、前記有機ケイ素化合物（ａ）で挙げた加水分解性基と同様のものが挙げられ、炭素数１～４のアルコキシ基が好ましく、より好ましくは炭素数１～２のアルコキシ基である。有機ケイ素化合物（ａ）と金属化合物（ｂ）の加水分解性基は、同一であっても異なっていてもよいが、いずれも炭素数１～４のアルコキシ基であることが好ましい。 Examples of the hydrolyzable group of the metal compound (b) include the same hydrolyzable groups as mentioned for the organosilicon compound (a), preferably an alkoxy group having 1 to 4 carbon atoms, more preferably carbon It is an alkoxy group of the number 1 or 2. The hydrolyzable groups of the organosilicon compound (a) and the metal compound (b) may be the same or different, but both are preferably alkoxy groups having 1 to 4 carbon atoms.
　金属化合物（ｂ）の金属原子Ｍにおいて、加水分解性基が結合した結合手以外の結合手には、前記有機ケイ素化合物（ａ）の中心ケイ素原子に結合していてもよいシロキサン骨格含有基（好ましくは有機ケイ素化合物（ａ）のトリアルキルシリル基含有分子鎖の分子鎖を構成する元素数よりも少ない元素数のシロキサン骨格含有基）；前記有機ケイ素化合物（ａ）の中心ケイ素原子に結合していてもよい炭化水素鎖含有基（好ましくは有機ケイ素化合物（ａ）のトリアルキルシリル基含有分子鎖の分子鎖を構成する元素数よりも少ない炭素数の炭化水素鎖を含有する炭化水素鎖含有基）；水素原子が結合していてもよく、上記有機ケイ素化合物（ａ）で説明した範囲から適宜選択でき、その結合数は１以下が好ましく、０であることが特に好ましい。 In the metal atom M of the metal compound (b), a siloxane skeleton-containing group (which may be bonded to the central silicon atom of the organosilicon compound (a)) may be bonded to a bond other than the bond to which the hydrolyzable group is bonded ( Preferably a siloxane skeleton-containing group having an element number smaller than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain of the organosilicon compound (a); and bonded to the central silicon atom of the organosilicon compound (a) A hydrocarbon chain-containing group (preferably containing a hydrocarbon chain having a number of carbon atoms smaller than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain of the organosilicon compound (a). Group); a hydrogen atom may be bonded, and can be appropriately selected from the range described in the organosilicon compound (a), and the number of bonds is preferably 1 or less, particularly 0. Masui.
　金属化合物（ｂ）において、加水分解性基の個数は、好ましくは２以上であり、より好ましくは３以上であり、４以下であることが更に好ましい。 In the metal compound (b), the number of hydrolyzable groups is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or less.
　金属化合物（ｂ）としては、加水分解性基のみを有する化合物；シロキサン骨格含有基と加水分解性基を有する化合物；２個のシロキサン骨格含有基と加水分解性基を有する化合物；炭化水素鎖含有基と加水分解性基を有する化合物；２個の炭化水素鎖含有基と加水分解性基を有する化合物；水素原子と加水分解性基を有する化合物；水素原子、炭化水素鎖含有基及び加水分解性基を有する化合物等を挙げることができる。
　加水分解性基のみを有する化合物としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のテトラアルコキシシラン；トリエトキシアルミニウム、トリプロポキシアルミニウム、トリブトキシアルミニウム等のトリアルコキシアルミニウム；トリエトキシ鉄等のトリアルコキシ鉄；トリメトキシインジウム、トリエトキシインジウム、トリプロポキシインジウム、トリブトキシインジウム等のトリアルコキシインジウム；テトラメトキシハフニウム、テトラエトキシハフニウム、テトラプロポキシハフニウム、テトラブトキシハフニウム等のテトラアルコキシハフニウム；テトラメトキシチタン、テトラエトキシチタン、テトラプロポキシチタン、テトラブトキシチタン等のテトラアルコキシチタン；テトラメトキシスズ、テトラエトキシスズ、テトラプロポキシスズ、テトラブトキシスズ等のテトラアルコキシスズ；テトラメトキシジルコニウム、テトラエトキシジルコニウム、テトラプロポキシジルコニウム、テトラブトキシジルコニウム等のテトラアルコキシジルコニウム；ペンタメトキシタンタル、ペンタエトキシタンタル、ペンタプロポキシタンタル、ペンタブトキシタンタル等のペンタアルコキシタンタル；等が挙げられる。 As the metal compound (b), a compound having only a hydrolyzable group; a compound having a siloxane skeleton-containing group and a hydrolyzable group; a compound having two siloxane skeleton-containing groups and a hydrolyzable group; containing a hydrocarbon chain A compound having a group and a hydrolyzable group; a compound having two hydrocarbon chain-containing groups and a hydrolyzable group; a compound having a hydrogen atom and a hydrolyzable group; a hydrogen atom, a hydrocarbon chain-containing group and a hydrolyzable group Examples thereof include a compound having a group.
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, tributoxy indium; tetraalkoxy hafnium such as tetramethoxy hafnium, tetraethoxy hafnium, tetrapropoxy hafnium, tetrabutoxy hafnium; tetra; Tetraal such as methoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium Tetraalkoxy tin such as tetramethoxytin, tetraethoxytin, tetrapropoxytin, tetrabutoxytin; tetraalkoxyzirconium such as tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium; pentamethoxytantalum, pentaethoxy And pentaalkoxy tantalum such as tantalum, pentapropoxy tantalum and pentaboxy tantalum;
　シロキサン骨格含有基と加水分解性基を有する化合物としては、トリメチルシリルオキシトリメトキシシラン、トリメチルシリルオキシトリエトキシシラン、トリメチルシリルオキシトリプロポキシシラン等のトリメチルシリルオキシトリアルコキシシラン；等が挙げられる。
　２個のシロキサン骨格含有基と加水分解性基を有する化合物としては、ジ（トリメチルシリルオキシ）ジメトキシシラン、ジ（トリメチルシリルオキシ）ジエトキシシラン、ジ（トリメチルシリルオキシ）ジプロポキシシラン等のジ（トリメチルシリルオキシ）ジアルコキシシラン；等が挙げられる。 Examples of the compound having a siloxane skeleton-containing group and a hydrolyzable group include trimethylsilyloxytrialkoxysilane such as trimethylsilyloxytrimethoxysilane, trimethylsilyloxytriethoxysilane, and trimethylsilyloxytripropoxysilane.
Examples of the compound having two siloxane skeleton-containing groups and hydrolyzable groups include di (trimethylsilyloxy) such as di (trimethylsilyloxy) dimethoxysilane, di (trimethylsilyloxy) diethoxysilane, and di (trimethylsilyloxy) dipropoxysilane. Dialkoxysilane; and the like.
　炭化水素鎖含有基と加水分解性基を有する化合物としては、メチルトリメトキシシラン、エチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、メチルトリプロポキシシラン等のアルキルトリアルコキシシラン；ビニルトリメトキシシラン、ビニルトリエトキシシラン等のアルケニルトリアルコキシシラン；等が挙げられる。
　２個の炭化水素鎖含有基と加水分解性基を有する化合物としては、ジメチルジメトキシシラン、ジエチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジエトキシシラン等のジアルキルジアルコキシシラン；等が挙げられる。 Examples of the compound having a hydrocarbon chain-containing group and a hydrolyzable group include alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and methyltripropoxysilane; vinyltrimethoxy Alkenyl trialkoxysilanes such as silane and vinyltriethoxysilane;
Examples of the compound having two hydrocarbon chain-containing groups and a hydrolyzable group include dialkyl dialkoxysilanes such as dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, and diethyldiethoxysilane.
　水素原子と加水分解性基を有する化合物としては、トリメトキシシラン、トリエトキシシラン、トリプロポキシシラン等が挙げられる。
　水素原子、炭化水素鎖含有基及び加水分解性基を有する化合物としては、ジメトキシメチルシラン、ジエトキシメチルシラン等が挙げられる。 Examples of the compound having a hydrogen atom and a hydrolyzable group include trimethoxysilane, triethoxysilane, and tripropoxysilane.
Examples of the compound having a hydrogen atom, a hydrocarbon chain-containing group, and a hydrolyzable group include dimethoxymethylsilane and diethoxymethylsilane.
　金属化合物（ｂ）は、具体的には、下記式（Ｂ１）で表される化合物であることが好ましい。 Specifically, the metal compound (b) is preferably a compound represented by the following formula (B1).
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
［前記式（Ｂ１）中、ＭはＡｌ、Ｆｅ、Ｉｎ、Ｇｅ、Ｈｆ、Ｓｉ、Ｔｉ、Ｓｎ、Ｚｒ、または、Ｔａを表し、
　Ｚb1は、シロキサン骨格含有基、炭化水素鎖含有基又は水素原子を表し、
　複数のＡb1は、それぞれ独立に、加水分解性基を表し、
　ｍは、金属原子に応じて、３～５の整数を表し、
　ｒは０又は１である。］ [In the formula (B1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta,
Z b1 represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group or a hydrogen atom,
Several A <b1> represents a hydrolysable group each independently,
m represents an integer of 3 to 5, depending on the metal atom,
r is 0 or 1; ]
　上記式（Ｂ１）中のＺb1におけるシロキサン骨格含有基、炭化水素鎖含有基、及びＡb1の加水分解性基は、上記有機ケイ素化合物（ａ）で説明したシロキサン骨格含有基、炭化水素鎖含有基及び加水分解性基の中から適宜選択でき、好ましい範囲も同様である。 Siloxane skeleton-containing groups in Z b1 in the formula (B1), the hydrocarbon chain-containing group, and hydrolyzable groups A b1 is the organic silicon compound (a) siloxane skeleton-containing group described in, hydrocarbon chains containing A group and a hydrolyzable group can be appropriately selected, and preferred ranges are also the same.
　ｍは、金属原子に応じて、３～５の整数を表し、すなわち、金属原子Ｍの価数を表す。ｒは０であることが好ましい。特に、ＭがＳｉであり、ｒが０であり、かつＡb1が炭素数１～４のアルコキシ基であることが好ましく、すなわちテトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、又はテトラブトキシシランが好ましく、特にテトラメトキシシラン又はテトラエトキシシランが好ましい。 m represents an integer of 3 to 5, depending on the metal atom, that is, the valence of the metal atom M. r is preferably 0. In particular, M is Si, r is 0, and A b1 is preferably an alkoxy group having 1 to 4 carbon atoms, that is, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is Tetramethoxysilane or tetraethoxysilane is particularly preferable.
　金属化合物（ｂ）の量は、組成物１００質量％中、例えば０．３質量％以上であり、より好ましくは０．５質量％以上であり、また５質量％以下が好ましく、より好ましくは３質量％以下である。 The amount of the metal compound (b) is, for example, 0.3% by mass or more, more preferably 0.5% by mass or more, and preferably 5% by mass or less in 100% by mass of the composition, more preferably 3%. It is below mass%.
　本発明の混合組成物は、２種以上の金属化合物（ｂ）を用いてもよい。また、金属化合物（ｂ）は、組成物中において、縮合物となっていてもよい。 The mixed composition of the present invention may use two or more metal compounds (b). Further, the metal compound (b) may be a condensate in the composition.
　有機ケイ素化合物（ａ）と金属化合物（ｂ）との合計量は、組成物１００質量％に対して、０．５質量％以上であり、好ましくは０．８質量％以上であり、更に好ましくは１．０質量％以上であり、また５質量％以下が好ましく、より好ましくは４質量％以下であり、更に好ましくは３質量％以下である。 The total amount of the organosilicon compound (a) and the metal compound (b) is 0.5% by mass or more, preferably 0.8% by mass or more, more preferably 100% by mass. 1.0 mass% or more, 5 mass% or less is preferable, More preferably, it is 4 mass% or less, More preferably, it is 3 mass% or less.
　有機ケイ素化合物（ａ）に対する金属化合物（ｂ）のモル比（（ｂ）／（ａ））は、５以上が好ましく、より好ましくは１０以上であり、更に好ましくは１５以上であり、また４０以下が好ましく、より好ましくは３５以下であり、更に好ましくは３０以下である。 The molar ratio of the metal compound (b) to the organosilicon compound (a) ((b) / (a)) is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more, and 40 or less. Is more preferably 35 or less, and still more preferably 30 or less.
　３．溶媒
　３－１．溶媒（ｃ２）
　溶媒（ｃ２）の、２０℃における蒸気圧は０．０３２ｋＰａ以上１０ｋＰａ以下であり、かつｓｐ値は１１（ｃａｌ／ｃｍ3）1/2以下である。本発明の組成物は、このような溶媒（ｃ２）が、組成物中５質量％以上混合されている。このような特性を有する溶媒（ｃ２）は、有機ケイ素化合物（ａ）、金属化合物（ｂ）などの成分との相溶性が良好であることや、成膜した際に適度に蒸発するという特徴がある。この特徴により、得られる皮膜の膜組成分布が適切になり、さらに残存溶媒が低減されることで、耐温水性を良好にできる。 3. Solvent 3-1. Solvent (c2)
The vapor pressure of the solvent (c2) at 20 ° C. is from 0.032 kPa to 10 kPa, and the sp value is 11 (cal / cm 3 ) 1/2 or less. In the composition of the present invention, such a solvent (c2) is mixed in an amount of 5% by mass or more in the composition. The solvent (c2) having such characteristics is characterized by having good compatibility with components such as the organosilicon compound (a) and the metal compound (b), and that it evaporates moderately when deposited. is there. With this feature, the film composition distribution of the resulting film becomes appropriate, and the remaining solvent is reduced, so that the warm water resistance can be improved.
　溶媒（ｃ２）の蒸気圧（２０℃）は、好ましくは０．０５ｋＰａ以上であり、より好ましくは０．１ｋＰａ以上であり、また８ｋＰａ以下が好ましく、より好ましくは６ｋＰａ以下である。特に蒸気圧が６ｋＰａ以下である場合に、皮膜の外観が良好になるとともに、皮膜形成直後の滑落性も良好となり、例えば後述する実施例の方法と同様にして皮膜形成直後の滑落性を評価した際の滑落速度を１０ｍｍ／秒以上とすることができる。 The vapor pressure (20 ° C.) of the solvent (c2) is preferably 0.05 kPa or more, more preferably 0.1 kPa or more, and preferably 8 kPa or less, more preferably 6 kPa or less. In particular, when the vapor pressure is 6 kPa or less, the appearance of the film is improved, and the sliding property immediately after the film formation is also improved. For example, the sliding property immediately after the film formation was evaluated in the same manner as in Examples described later. The sliding speed at the time can be 10 mm / second or more.
　また、溶媒（ｃ２）のｓｐ値は１１（ｃａｌ／ｃｍ3）1/2以下である。本書において、ｓｐ値（Ｓｏｌｕｂｉｌｉｔｙ　Ｐａｒａｍｅｔｅｒ、溶解度パラメーター）とは、「Ｒ．Ｆ．Ｆｅｄｏｒｓ、Ｐｏｌｙｍ．Ｅｎｇ．Ｓｃｉ．，１４［２］、１４７－１５４（１９７４）」に記載の方法によって算出される値である。Ｆｅｄｏｒｓ法では、ｓｐ値は凝集エネルギー密度の平方根で定義される。具体的には、ｓｐ値は以下の式で定義される。
　δ＝（ΔＥ／Ｖ）1/2　　　（１）
　上記式（１）においてδはｓｐ値（（ｃａｌ／ｃｍ3）1/2）、ΔＥは凝集エネルギー（ｃａｌ／ｍｏｌ）、Ｖは溶媒のモル分子容（ｃｍ3／ｍｏｌ）を意味する。 Further, the sp value of the solvent (c2) is 11 (cal / cm 3 ) 1/2 or less. In this document, sp value (Solubility Parameter, solubility parameter) is a value calculated by the method described in “RF Fedors, Polym. Eng. Sci., 14 [2], 147-154 (1974)”. It is. In the Fedors method, the sp value is defined by the square root of the cohesive energy density. Specifically, the sp value is defined by the following equation.
δ = (ΔE / V) 1/2 (1)
In the above formula (1), δ means the sp value ((cal / cm 3 ) 1/2 ), ΔE means the cohesive energy (cal / mol), and V means the molar molecular volume (cm 3 / mol) of the solvent.
　Ｆｅｄｏｒｓ法では、上記した凝集エネルギーとモル分子容がいずれも、溶媒に含まれる置換基の種類と数に依存していると考えられている。従って、凝集エネルギーの算出は、各置換基が有する凝集エネルギーと分子容（下記表５に示す）から、置換基の個数も考慮して算出される。 In the Fedors method, it is considered that both the above-described cohesive energy and molar molecular volume depend on the type and number of substituents contained in the solvent. Accordingly, the calculation of the cohesive energy is performed in consideration of the number of substituents from the cohesive energy and molecular volume (shown in Table 5 below) of each substituent.
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
　例えば、本発明において好ましい溶媒（ｃ２）として用いられる酢酸ブチルは、－ＣＨ3を２個、－ＣＨ2－を３個、－ＣＯＯ－を１個有する溶媒である。
　酢酸ブチルの凝集エネルギーΔＥは、
　ΔＥ（ｃａｌ／ｍｏｌ）＝１１２５×２＋１１８０×３＋４３００×１
と算出される。
　また、酢酸ブチルのモル分子容Ｖは
　Ｖ（ｃｍ3／ｍｏｌ）＝３３．５×２＋１６．１×３＋１８×１
と算出される。
　従って、前記式（１）にこれら値を用いることにより、酢酸ブチルのｓｐ値は８．７０（ｃａｌ／ｃｍ3）1/2と算出できる。 For example, butyl acetate used as the preferred solvent (c2) in the present invention is a solvent having two —CH 3 , three —CH 2 —, and one —COO—.
The cohesive energy ΔE of butyl acetate is
ΔE (cal / mol) = 1125 × 2 + 1180 × 3 + 4300 × 1
Is calculated.
The molar molecular volume V of butyl acetate is V (cm 3 /mol)=33.5×2+16.1×3+18×1
Is calculated.
Therefore, by using these values in the formula (1), the sp value of butyl acetate can be calculated as 8.70 (cal / cm 3 ) 1/2 .
　溶媒（ｃ２）のｓｐ値は、好ましくは１０．５（ｃａｌ／ｃｍ3）1/2以下であり、より好ましくは１０（ｃａｌ／ｃｍ3）1/2以下であり、また５（ｃａｌ／ｃｍ3）1/2以上が好ましく、より好ましくは６（ｃａｌ／ｃｍ3）1/2以上である。 The sp value of the solvent (c2) is preferably 10.5 (cal / cm 3 ) 1/2 or less, more preferably 10 (cal / cm 3 ) 1/2 or less, and 5 (cal / cm 3 ). 3 ) 1/2 or more is preferable, more preferably 6 (cal / cm 3 ) 1/2 or more.
　溶媒（ｃ２）の大気圧における沸点は、例えば８５℃以上であり、好ましくは９０℃以上であり、より好ましくは１００℃以上であり、また１９０℃以下が好ましく、より好ましくは１８０℃以下である。 The boiling point of the solvent (c2) at atmospheric pressure is, for example, 85 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and preferably 190 ° C. or lower, more preferably 180 ° C. or lower. .
　また、溶媒（ｃ２）の２０℃における水の溶解度は、例えば２３０ｇ／Ｌ以下であり、下限は特に限定されないが１ｇ／Ｌ以上であってもよい。 Moreover, the solubility of water at 20 ° C. in the solvent (c2) is, for example, 230 g / L or less, and the lower limit is not particularly limited, but may be 1 g / L or more.
　溶媒（ｃ２）としては、酢酸イソプロピル、酢酸ブチル、酢酸２－エトキシエチルなどが挙げられる。 Examples of the solvent (c2) include isopropyl acetate, butyl acetate, 2-ethoxyethyl acetate and the like.
　溶媒（ｃ２）の量は、組成物１００質量％に対して、５質量％以上であり、このようにすることで得られる皮膜の耐温水性が良好になる。溶媒（ｃ２）の量は、２３．０質量％以上であることが好ましく、このようにすることで、耐温水性を一層向上できる。（ｃ２）の量は、３０質量％以上であることがより好ましく、４０質量％以上であることがさらに好ましく、よりさらに好ましくは５０質量％以上であり、特に好ましくは５５質量％以上であり、上限は例えば９８質量％以下である。特に、溶媒（ｃ２）の量を５５質量％以上にすることで、皮膜の外観を良好にできるため好ましい。 The amount of the solvent (c2) is 5% by mass or more with respect to 100% by mass of the composition, and the warm water resistance of the film obtained in this way is improved. The amount of the solvent (c2) is preferably 23.0% by mass or more, and by doing so, the warm water resistance can be further improved. The amount of (c2) is more preferably 30% by mass or more, further preferably 40% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more. The upper limit is, for example, 98% by mass or less. In particular, the amount of the solvent (c2) is preferably 55% by mass or more because the appearance of the film can be improved.
　本発明の混合組成物は、２種以上の溶媒（ｃ２）を用いてもよい。 The mixed composition of the present invention may use two or more solvents (c2).
　３－２．溶媒（ｃ１）
　得られる皮膜の耐温水性をより良好にするため（好ましくは、皮膜の透明性も良好にするため）、本発明の組成物は、溶媒（ｃ２）と共に、２０℃における水の溶解度が２３１ｇ／Ｌ以上であり、かつｓｐ値が２０以下である溶媒（ｃ１）が混合されていることが好ましい。溶媒（ｃ１）の２０℃での水の溶解度は、２５０ｇ／Ｌ以上が好ましく、より好ましくは３００ｇ／Ｌ以上であり、上限は特に限定されず、溶媒（ｃ１）と水が任意の割合で混和できることが好ましい。溶媒（ｃ１）のｓｐ値は１８（ｃａｌ／ｃｍ3）1/2以下が好ましく、より好ましくは１６（ｃａｌ／ｃｍ3）1/2以下であり、また１１（ｃａｌ／ｃｍ3）1/2超であることが好ましい。 3-2. Solvent (c1)
In order to improve the warm water resistance of the resulting film (preferably also to improve the transparency of the film), the composition of the present invention has a water solubility at 20 ° C. of 231 g / in with the solvent (c2). It is preferable that a solvent (c1) having an L value of not less than L and an sp value of not more than 20 is mixed. The solubility of water at 20 ° C. of the solvent (c1) is preferably 250 g / L or more, more preferably 300 g / L or more, and the upper limit is not particularly limited, and the solvent (c1) and water are mixed at an arbitrary ratio. Preferably it can be done. The sp value of the solvent (c1) is preferably 18 (cal / cm 3 ) 1/2 or less, more preferably 16 (cal / cm 3 ) 1/2 or less, and 11 (cal / cm 3 ) 1/2. It is preferable that it is super.
　溶媒（ｃ１）の大気圧での沸点は、例えば８５℃未満であり、好ましくは８３℃以下であり、下限は例えば６０℃以上である。 The boiling point of the solvent (c1) at atmospheric pressure is, for example, less than 85 ° C., preferably 83 ° C. or less, and the lower limit is, for example, 60 ° C. or more.
　溶媒（ｃ１）としては、イソプロパノール、エタノール、メタノール、メチルエチルケトンなどが挙げられる。 Examples of the solvent (c1) include isopropanol, ethanol, methanol, and methyl ethyl ketone.
　溶媒（ｃ１）の量は、組成物１００質量％に対して１質量％以上が好ましく、より好ましくは２質量％以上であり、更に好ましくは５質量％以上であり、また５０質量％以下が好ましく、より好ましくは４５質量％以下であり、更に好ましくは４０質量％以下である。 The amount of the solvent (c1) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, and preferably 50% by mass or less with respect to 100% by mass of the composition. More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less.
　溶媒（ｃ１）に対する溶媒（ｃ２）の質量比（ｃ２／ｃ１）は、１以上が好ましく、より好ましくは３以上であり、更に好ましくは１０以上であり、また４５以下が好ましく、より好ましくは４０以下である。 The mass ratio (c2 / c1) of the solvent (c2) to the solvent (c1) is preferably 1 or more, more preferably 3 or more, still more preferably 10 or more, and preferably 45 or less, more preferably 40. It is as follows.
　本発明の組成物に溶媒（ｃ１）が混合されている場合、２種以上の溶媒（ｃ１）を用いてもよい。 When the solvent (c1) is mixed in the composition of the present invention, two or more solvents (c1) may be used.
　本発明の組成物は、ゾルゲル法で一般的に用いられる酸触媒、塩基触媒、有機金属触媒のいずれかが混合されていてもよい。酸触媒としては、塩酸、硝酸、硫酸、リン酸等の無機酸；クエン酸、シュウ酸、酢酸などの有機酸が挙げられる。塩基触媒としては、アンモニア、アミン類などが挙げられる。有機金属触媒としては、Ａｌ、Ｆｅ、Ｚｎ、Ｓｎ、Ｚｒ等の金属元素を中心金属とする有機金属化合物が挙げられ、アルミニウムアセチルアセトン錯体、アルミニウムエチルアセトアセテート錯体等の有機アルミニウム化合物；オクチル酸鉄等の有機鉄化合物；亜鉛アセチルアセトナートモノハイドレート、ナフテン酸亜鉛、オクチル酸亜鉛等の有機亜鉛化合物；ジブチル錫ジアセテート錯体等の有機錫化合物；などが挙げられる。触媒は、酸触媒が好ましく、特に酢酸等の有機酸触媒が好ましい。触媒の量は、組成物１００質量％中、例えば０．１～０．５質量％である。 The composition of the present invention may be mixed with any of an acid catalyst, a base catalyst, and an organometallic catalyst that are generally used in the sol-gel method. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; and organic acids such as citric acid, oxalic acid, and acetic acid. Examples of the base catalyst include ammonia and amines. Examples of the organometallic catalyst include organometallic compounds having a metal element such as Al, Fe, Zn, Sn, and Zr as a central metal, and organoaluminum compounds such as aluminum acetylacetone complex and aluminum ethylacetoacetate complex; iron octylate and the like Organic zinc compounds such as zinc acetylacetonate monohydrate, zinc naphthenate and zinc octylate; organic tin compounds such as dibutyltin diacetate complex; The catalyst is preferably an acid catalyst, particularly an organic acid catalyst such as acetic acid. The amount of the catalyst is, for example, 0.1 to 0.5% by mass in 100% by mass of the composition.
　また、本発明の組成物は、水が混合されていてもよく、水の量は溶媒に均一に溶解させることが出来る範囲であれば、任意に選択することができる。例えば組成物１００質量％中、０．５質量％以下であることが好ましい。水の量を適宜コントロールすることによって、反応液の均一性が向上し、調液再現性が向上することが期待できる。水の量は、好ましくは０．３質量％以下であり、より好ましくは０．２質量％以下であり、また０．０１質量％以上であってもよい。また、溶媒（ｃ１）と（ｃ２）の合計１００質量部（溶媒（ｃ１）を用いない場合には、溶媒（ｃ２）のみの量）に対する水の割合は０．０１質量部以上が好ましく、また０．３質量部以下が好ましい。 Further, the composition of the present invention may be mixed with water, and the amount of water can be arbitrarily selected as long as it can be uniformly dissolved in a solvent. For example, it is preferable that it is 0.5 mass% or less in 100 mass% of compositions. By appropriately controlling the amount of water, it can be expected that the uniformity of the reaction solution is improved and the reproducibility of preparation is improved. The amount of water is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and may be 0.01% by mass or more. Further, the ratio of water to the total of 100 parts by mass of the solvents (c1) and (c2) (in the case where the solvent (c1) is not used, only the amount of the solvent (c2)) is preferably 0.01 parts by mass or more. 0.3 mass part or less is preferable.
　水の量は、有機ケイ素化合物（ａ）と金属化合物（ｂ）との合計量に対して調整することも好ましく、有機ケイ素化合物（ａ）と金属化合物（ｂ）の合計モル量に対する水のモル量の比は、０．１以上が好ましく、０．１２以上がより好ましく、更に好ましくは０．２以上であり、また１０以下が好ましく、より好ましくは５以下であり、更に好ましくは３以下であり、特に好ましくは２以下である。 The amount of water is preferably adjusted with respect to the total amount of the organosilicon compound (a) and the metal compound (b), and the mole of water relative to the total molar amount of the organosilicon compound (a) and the metal compound (b). The ratio of the amount is preferably 0.1 or more, more preferably 0.12 or more, further preferably 0.2 or more, and preferably 10 or less, more preferably 5 or less, still more preferably 3 or less. Yes, particularly preferably 2 or less.
　本発明の組成物は、本発明の効果を阻害しない範囲で、酸化防止剤、防錆剤、紫外線吸収剤、光安定剤、防カビ剤、抗菌剤、生物付着防止剤、消臭剤、顔料、難燃剤、帯電防止剤等、各種の添加剤が混合されていてもよい。 The composition of the present invention is an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-bioadhesive agent, a deodorant and a pigment as long as the effects of the present invention are not impaired Various additives such as a flame retardant and an antistatic agent may be mixed.
　本発明の混合組成物の作製手順は例えば以下の通りである。まず、有機ケイ素化合物（ａ）と金属化合物（ｂ）とを溶媒に溶解させる。このとき、５～３０分程度撹拌することが好ましい。続いて、必要に応じて触媒（好ましくは酸触媒）を添加した後、１～２４時間ほど撹拌する（好ましくは４０～７０℃程度の加熱しながら撹拌する）。こうすることで、有機ケイ素化合物（ａ）及び金属化合物（ｂ）に含まれる加水分解性基の一部が、空気中の水分や、必要に応じて用いられる触媒に含まれる水分などによって、加水分解・脱水縮合反応を起こす。有機ケイ素化合物（ａ）と金属化合物（ｂ）とを溶解させる溶媒（以下、「反応溶媒」と呼ぶ場合がある）として、前記した（ｃ１）溶媒を用いることが好ましい。（ｃ１）溶媒を用いることで、均一な溶液を調製することができる。更に、得られた溶液に前記溶媒（ｃ２）を添加して希釈し、塗布溶液（本発明の混合組成物）を作製する。塗布溶液に溶媒（ｃ２）が混合されていることで、基材に塗布した後の溶媒の揮発が適切に調整でき、得られる皮膜の透明性及び耐温水性が良好になる。希釈溶媒は、溶媒（ｃ２）が混合されている限り、他の溶媒が混合されていてもよく、希釈溶媒は溶媒（ｃ２）と溶媒（ｃ１）が混合されたものでもよい。 For example, the preparation procedure of the mixed composition of the present invention is as follows. First, the organosilicon compound (a) and the metal compound (b) are dissolved in a solvent. At this time, it is preferable to stir for about 5 to 30 minutes. Subsequently, if necessary, a catalyst (preferably an acid catalyst) is added, followed by stirring for 1 to 24 hours (preferably stirring while heating at about 40 to 70 ° C.). In this way, some of the hydrolyzable groups contained in the organosilicon compound (a) and the metal compound (b) are hydrolyzed by moisture in the air or moisture contained in the catalyst used as necessary. Causes decomposition and dehydration condensation reactions. As the solvent for dissolving the organosilicon compound (a) and the metal compound (b) (hereinafter sometimes referred to as “reaction solvent”), it is preferable to use the solvent (c1) described above. (C1) A uniform solution can be prepared by using a solvent. Furthermore, the said solvent (c2) is added and diluted to the obtained solution, and a coating solution (mixed composition of this invention) is produced. By mixing the solvent (c2) with the coating solution, the volatilization of the solvent after coating on the substrate can be appropriately adjusted, and the transparency and warm water resistance of the resulting film are improved. As long as the solvent (c2) is mixed, the diluting solvent may be mixed with another solvent, and the diluting solvent may be a mixture of the solvent (c2) and the solvent (c1).
　また、本発明の混合組成物を基材と接触させる方法としては、例えば組成物を基材にコーティングする方法が挙げられ、スピンコーティング法、ディップコーティング法、スプレーコーティング法、ロールコート法、バーコート法、手塗り(布等に液を染み込ませ、基材に塗りこむ方法)、かけ流し(液をスポイトなどを用いて基材にそのままかけ、塗布する方法)、霧吹き（霧吹きを用いて基材に塗布する方法）などが挙げられる。本発明の混合組成物を基材と接触させた状態で、空気中、常温で静置（例えば０．５時間～４８時間、好ましくは１０時間～４８時間）するか又は１～１０時間程度加熱（例えば３００℃以下）することで、加水分解性基の加水分解・重縮合が促進され、基材上に皮膜を形成できる。 Examples of the method of bringing the mixed composition of the present invention into contact with the substrate include a method of coating the substrate with the composition, such as spin coating, dip coating, spray coating, roll coating, bar coating. Method, hand-coating (a method of soaking a liquid in a cloth and applying to a base material), pouring (a method of applying the liquid as it is to a base material using a dropper, etc.), spraying (a base material using a spray) And the like). Leave the mixed composition of the present invention in contact with the base material in air at room temperature (for example, 0.5 to 48 hours, preferably 10 to 48 hours) or heat for about 1 to 10 hours. By performing (for example, 300 ° C. or less), hydrolysis / polycondensation of the hydrolyzable group is promoted, and a film can be formed on the substrate.
　本発明の混合組成物から形成される皮膜の膜厚は、塗布方法にもよるが、例えば０．５～１００ｎｍ程度とできる。また、該皮膜について、後述の実施例の方法で評価される水滴の接触角は、例えば９５°～１１０°（好ましくは９８°～１０８°）である。また、後述の実施例の方法で評価される皮膜のヘーズは例えば１．４％以下であり、好ましくは１．０％以下であり、より好ましくは０．８％以下であり、さらに好ましくは０．６％以下であり、特に好ましくは０．３％以下である。下限は特に限定されないが例えば０．０１％程度である。更に、後述する方法で評価される温水試験後の皮膜における水滴の接触角は、例えば９５°～１１３°（好ましくは９８°～１１０°）である。また、温水試験後の皮膜の滑落速度は、例えば５ｍｍ／秒以上であり、好ましくは１０ｍｍ／秒以上であり、より好ましくは１５ｍｍ／秒以上であり、更に好ましくは２０ｍｍ／秒以上であり、上限は特に限定されないが、例えば１００ｍｍ／秒以下である。 The film thickness of the film formed from the mixed composition of the present invention can be, for example, about 0.5 to 100 nm, although it depends on the coating method. Further, the contact angle of water droplets evaluated by the method of Examples described later for the film is, for example, 95 ° to 110 ° (preferably 98 ° to 108 °). Further, the haze of the film evaluated by the method of Examples described later is, for example, 1.4% or less, preferably 1.0% or less, more preferably 0.8% or less, and further preferably 0. .6% or less, particularly preferably 0.3% or less. Although a minimum is not specifically limited, For example, it is about 0.01%. Furthermore, the contact angle of water droplets in the film after the hot water test evaluated by the method described later is, for example, 95 ° to 113 ° (preferably 98 ° to 110 °). Further, the sliding speed of the film after the hot water test is, for example, 5 mm / second or more, preferably 10 mm / second or more, more preferably 15 mm / second or more, further preferably 20 mm / second or more, and the upper limit. Is not particularly limited, but is, for example, 100 mm / second or less.
　本発明の混合組成物を接触させる基材は特に限定されず、基材の形状は平面、曲面のいずれでもよいし、多数の面が組み合わさった三次元的構造でもよい。また基材の材質も限定されず、有機系材料、無機系材料のいずれで構成されていてもよい。前記有機系材料としては、アクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂、スチレン樹脂、アクリル－スチレン共重合樹脂、セルロース樹脂、ポリオレフィン樹脂等の熱可塑性樹脂；フェノール樹脂、ユリア樹脂、メラミン樹脂、エポキシ樹脂、不飽和ポリエステル、シリコーン樹脂、ウレタン樹脂等の熱硬化性樹脂；等が挙げられ、無機系材料としては、セラミックス；ガラス；鉄、シリコン、銅、亜鉛、アルミニウム等の金属；前記金属を含む合金；等が挙げられる。 The substrate to which the mixed composition of the present invention is contacted is not particularly limited, and 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. Further, the material of the base material is not limited and may be composed of either an organic material or an inorganic material. Examples of the organic material include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, and polyolefin resin; phenol resin, urea resin, melamine resin, epoxy resin, Examples of inorganic materials include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the above metals; etc. Is mentioned.
　前記基材には予め易接着処理を施しておいてもよい。易接着処理としては、コロナ処理、プラズマ処理、紫外線処理等の親水化処理が挙げられる。また、樹脂、シランカップリング剤、テトラアルコキシシラン等によるプライマー処理を用いてもよい。また、樹脂、シランカップリング剤、テトラアルコキシシラン等によるプライマー処理を施しても良いし、ポリシラザンなどのガラス皮膜を基材に予め塗布しておいても良い。 The substrate may be subjected to an easy adhesion treatment in advance. Examples of the easy adhesion treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment. Further, primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, or the like may be used. In addition, primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, or the like may be performed, or a glass film such as polysilazane may be applied to the substrate in advance.
　以下、実施例を挙げて本発明をより具体的に説明する。本発明は以下の実施例によって制限を受けるものではなく、前記、後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples, and can of course be implemented with appropriate modifications within a range that can be adapted to the above-described gist. Included in the range.
　以下の実施例及び比較例は、下記の方法により評価した。 The following examples and comparative examples were evaluated by the following methods.
　（１）接触角の測定
　接触角測定装置（ＤＭ７００、協和界面科学社製）を用い、液滴法（解析方法：θ／２法、水滴量：３．０μＬ）にて、皮膜表面の接触角を測定した。 (1) Contact angle measurement Using a contact angle measurement device (DM700, manufactured by Kyowa Interface Science Co., Ltd.), the droplet surface (analysis method: θ / 2 method, water droplet amount: 3.0 μL) is used to contact the surface of the film surface. Was measured.
　（２）ヘーズの測定
　ヘーズメーターＨＺ－２（スガ試験機）を用い、Ｄ６５光源（平均昼光）にて、皮膜表面のヘーズ（曇り度）を測定した。 (2) Measurement of haze The haze (cloudiness) of the film surface was measured with a D65 light source (average daylight) using a haze meter HZ-2 (Suga Test Instruments).
　（３）耐温水性試験
　試料を７０℃のイオン交換水に１２時間浸漬し、前記（１）と同様に接触角を測定するとともに、皮膜表面に水滴を滴下したときの滑落速度によって水滴の滑落性を評価した。滑落速度は、接触角測定装置（ＤＭ７００、協和界面科学社製）を用い、２０°に傾けた基板上の皮膜表面に５０μＬの水滴を滴下し、初期滴下位置から水滴が１．５ｃｍ滑落する時間を測定することで算出した。 (3) Warm water resistance test The sample was immersed in ion-exchanged water at 70 ° C. for 12 hours, and the contact angle was measured in the same manner as in (1) above. Sex was evaluated. The sliding speed was measured by dropping 50 μL of water droplets onto the surface of the film on the substrate inclined at 20 ° using a contact angle measuring device (DM700, manufactured by Kyowa Interface Science Co., Ltd.) It was calculated by measuring.
　実施例１
　上記の式（Ａ－Ｉ－２６）におけるｎ１０の平均値が２４である化合物（１）０．２９ｇ、テトラエトキシシラン０．７１ｇを、イソプロパノール２．１３ｇに溶解させた。得られた溶液に触媒としての酢酸０．０００８ｇと水０．１４ｇを滴下した後、６５℃で４時間撹拌して試料溶液を作製した。前記試料溶液１を、酢酸ブチル６６．８８ｇで希釈し、塗布溶液１とした。 Example 1
In the above formula (AI-26), 0.29 g of the compound (1) having an average value of n10 of 24 and 0.71 g of tetraethoxysilane were dissolved in 2.13 g of isopropanol. To the obtained solution, 0.0008 g of acetic acid as a catalyst and 0.14 g of water were dropped, and then stirred at 65 ° C. for 4 hours to prepare a sample solution. The sample solution 1 was diluted with 66.88 g of butyl acetate to obtain a coating solution 1.
　塗布溶液１を、プラズマ処理を行った無アルカリガラス（イーグルＸＧ）に、スピンコータ（ＭＩＫＡＳＡ社製）により、回転数３０００ｒｐｍ、２０ｓｅｃの条件で製膜した後、２００℃３ｈ熱処理を行ってサンプルを得た。 The coating solution 1 is formed on a non-alkali glass (Eagle XG) that has been plasma-treated by a spin coater (manufactured by MIKASA) under the conditions of a rotational speed of 3000 rpm and 20 seconds, and then heat treated at 200 ° C. for 3 hours to obtain a sample. It was.
　実施例２
　前記試料溶液を酢酸２－エトキシエチル７４．１０ｇで希釈して塗布溶液２を作製したこと以外は実施例１と同様にして、基材上に皮膜を形成した。 Example 2
A film was formed on the substrate in the same manner as in Example 1 except that the coating solution 2 was prepared by diluting the sample solution with 74.10 g of 2-ethoxyethyl acetate.
　実施例３
　前記試料溶液作製時の撹拌時間を６時間とし、試料溶液をイソプロパノール２３．７４ｇと酢酸２－エトキシエチル４４．４６ｇの混合液で希釈して塗布溶液３を作製したこと以外は実施例１と同様にして、基材上に皮膜を形成した。 Example 3
The same as in Example 1, except that the stirring time in the preparation of the sample solution was 6 hours and the sample solution was diluted with a mixed solution of 23.74 g of isopropanol and 44.46 g of 2-ethoxyethyl acetate to prepare the coating solution 3. Thus, a film was formed on the substrate.
　実施例４
　前記試料溶液作製時の撹拌時間を６時間とし、試料溶液をイソプロパノール１１．８７ｇと酢酸２－エトキシエチル５９．２８ｇの混合液で希釈して塗布溶液４を作製したこと以外は実施例１と同様にして、基材上に皮膜を形成した。 Example 4
The same as in Example 1, except that the stirring time for the preparation of the sample solution was 6 hours and the sample solution was diluted with a mixed solution of 11.87 g of isopropanol and 59.28 g of 2-ethoxyethyl acetate to prepare the coating solution 4. Thus, a film was formed on the substrate.
　実施例５
　上記の式（Ａ－Ｉ－２６）におけるｎ１０の平均値が２４である化合物（１）０．２１ｇ、テトラエトキシシラン０．５３ｇを、イソプロパノール１．４９ｇに溶解させ、室温で２０分撹拌した。得られた溶液に触媒としての酢酸０．０００８ｇと水０．１４ｇを滴下した後、室温で４時間撹拌して試料溶液を作製した。前記試料溶液を、酢酸２－エトキシエチル５５．５８ｇで希釈し、塗布溶液５とした。塗布溶液５を実施例１と同様にして基材に塗布し、基材上に皮膜を形成した。 Example 5
In the above formula (AI-26), 0.21 g of the compound (1) having an average value of n10 of 24 and 0.53 g of tetraethoxysilane were dissolved in 1.49 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0008 g of acetic acid as a catalyst and 0.14 g of water were dropped, and then stirred at room temperature for 4 hours to prepare a sample solution. The sample solution was diluted with 55.58 g of 2-ethoxyethyl acetate to obtain a coating solution 5. The coating solution 5 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
　実施例６
　前記試料溶液作製時の撹拌時間を６時間とし、試料溶液をイソプロパノール８．９０ｇと酢酸２－エトキシエチル４４．４６ｇの混合液で希釈して塗布溶液６を作製したこと以外は実施例５と同様にして、基材上に皮膜を形成した。 Example 6
The same as in Example 5 except that the stirring time for the preparation of the sample solution was 6 hours, and the coating solution 6 was prepared by diluting the sample solution with a mixed solution of 8.90 g of isopropanol and 44.46 g of 2-ethoxyethyl acetate. Thus, a film was formed on the substrate.
　実施例７
　上記の式（Ａ－Ｉ－２６）におけるｎ１０の平均値が２４である化合物（１）０．２２ｇ、テトラエトキシシラン０．５５ｇを、イソプロパノール１．３４ｇに溶解させ、室温で２０分撹拌した。得られた溶液に触媒としての酢酸０．０００８ｇと水０．１４ｇを滴下した後、室温で６時間撹拌して試料溶液を作製した。前記試料溶液を、酢酸２－エトキシエチル５５．５８ｇで希釈し、塗布溶液７とした。塗布溶液７を実施例１と同様にして基材に塗布し、基材上に皮膜を形成した。 Example 7
In the above formula (AI-26), 0.22 g of compound (1) having an average value of n10 of 24 and 0.55 g of tetraethoxysilane were dissolved in 1.34 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0008 g of acetic acid as a catalyst and 0.14 g of water were dropped, and then stirred at room temperature for 6 hours to prepare a sample solution. The sample solution was diluted with 55.58 g of 2-ethoxyethyl acetate to obtain a coating solution 7. The coating solution 7 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
　実施例８
　上記の式（Ａ－Ｉ－２６）におけるｎ１０の平均値が２４である化合物（１）０．２９ｇ、テトラエトキシシラン０．７１ｇを、イソプロパノール２．１３ｇに溶解させ、室温で２０分撹拌した。得られた溶液に触媒としての酢酸０．０００８ｇと水０．１４ｇを滴下した後、室温で４時間撹拌して試料溶液を作製した。前記試料溶液を、酢酸イソプロピル６６．８８ｇで希釈し、塗布溶液８とした。塗布溶液８を実施例１と同様にして基材に塗布し、基材上に皮膜を形成した。 Example 8
In the above formula (AI-26), 0.29 g of the compound (1) having an average value of n10 of 24 and 0.71 g of tetraethoxysilane were dissolved in 2.13 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0008 g of acetic acid as a catalyst and 0.14 g of water were dropped, and then stirred at room temperature for 4 hours to prepare a sample solution. The sample solution was diluted with 66.88 g of isopropyl acetate to obtain a coating solution 8. The coating solution 8 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
　実施例９
　前記試料溶液作製時の混合時間を６時間とし、試料溶液をイソパノール２９．６８ｇと酢酸２－エトキシエチル３７．０５ｇの混合液で希釈して塗布溶液９を作製したこと以外は実施例８と同様にして基材上に皮膜を形成した。 Example 9
The same as in Example 8 except that the mixing time for preparing the sample solution was 6 hours and the sample solution was diluted with a mixed solution of 29.68 g of isopanol and 37.05 g of 2-ethoxyethyl acetate to prepare the coating solution 9. Thus, a film was formed on the substrate.
　実施例１０
　前記試料溶液作製時の混合時間を６時間とし、試料溶液をイソプロパノール４７．４８ｇと酢酸２－エトキシエチル１４．８２ｇの混合液で希釈して塗布溶液１０を作製したこと以外は、実施例８と同様にして基材上に皮膜を形成した。 Example 10
Example 8 is the same as Example 8 except that the mixing time for preparing the sample solution was 6 hours and the sample solution was diluted with a mixed solution of 47.48 g of isopropanol and 14.82 g of 2-ethoxyethyl acetate to prepare the coating solution 10. Similarly, a film was formed on the substrate.
　実施例１１
　上記の式（Ａ－Ｉ－２６）におけるｎ１０の平均値が２４である化合物（１）０．４３ｇ、テトラエトキシシラン０．３８ｇを、イソプロパノール２．０４ｇに溶解させ、室温で２０分撹拌した。得られた溶液に触媒としての酢酸０．０００８ｇと水０．１４ｇを滴下した後、室温で４時間撹拌して試料溶液を作製した。前記試料溶液を、酢酸２－エトキシエチル８４．９０ｇで希釈し、塗布溶液１１とした。塗布溶液１１を実施例１と同様にして基材に塗布し、基材上に皮膜を形成した。 Example 11
In the above formula (AI-26), 0.43 g of compound (1) having an average value of n10 of 24 and 0.38 g of tetraethoxysilane were dissolved in 2.04 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0008 g of acetic acid as a catalyst and 0.14 g of water were dropped, and then stirred at room temperature for 4 hours to prepare a sample solution. The sample solution was diluted with 84.90 g of 2-ethoxyethyl acetate to obtain a coating solution 11. The coating solution 11 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
　実施例１２
　酢酸２－エトキシエチル８４．９０ｇに代えて、酢酸２－メトキシ－１－メチルエチル８４．３９ｇを用いて塗布溶液１２を作製したこと以外は、実施例１１と同様にして基材上に皮膜を形成した。 Example 12
A coating was formed on the substrate in the same manner as in Example 11, except that 84.39 g of 2-methoxy-1-methylethyl acetate was used instead of 84.90 g of 2-ethoxyethyl acetate. Formed.
　実施例１３
　上記の式（Ａ－Ｉ－２６）におけるｎ１０の平均値が４５である化合物（２）０．５３ｇ、テトラエトキシシラン０．２９ｇを、イソプロパノール２．０７ｇに溶解させ、室温で２０分撹拌した。得られた溶液に触媒としての酢酸０．０００６ｇと水０．１０ｇを滴下した後、室温で４時間撹拌して試料溶液を作製した。前記試料溶液を、酢酸２－エトキシエチル８４．９０ｇで希釈し、塗布溶液１３とした。塗布溶液１３を実施例１と同様にして基材に塗布し、基材上に皮膜を形成した。 Example 13
In the above formula (AI-26), 0.53 g of the compound (2) having an average value of n10 of 45 and 0.29 g of tetraethoxysilane were dissolved in 2.07 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0006 g of acetic acid as a catalyst and 0.10 g of water were dropped, and then stirred at room temperature for 4 hours to prepare a sample solution. The sample solution was diluted with 84.90 g of 2-ethoxyethyl acetate to obtain a coating solution 13. The coating solution 13 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
　実施例１４
　酢酸２－エトキシエチル８４．９０ｇに代えて、酢酸２－メトキシ－１－メチルエチル８４．３９ｇを用いて塗布溶液１４を作製したこと以外は、実施例１３と同様にして基材上に皮膜を形成した。 Example 14
A coating film was formed on the substrate in the same manner as in Example 13 except that 84.39 g of 2-methoxy-1-methylethyl acetate was used instead of 84.90 g of 2-ethoxyethyl acetate. Formed.
　実施例１５
　上記の式（Ａ－Ｉ－２６）におけるｎ１０の平均値が４５である化合物（２）０．２８ｇ、テトラエトキシシラン０．５４ｇを、イソプロパノール２．０１ｇに溶解させ、室温で２０分撹拌した。得られた溶液に触媒としての酢酸０．００１１ｇと水０．１８ｇを滴下した後、室温で４時間撹拌して試料溶液を作製した。前記試料溶液を、酢酸２－エトキシエチル８４．９０ｇで希釈し、塗布溶液１５とした。塗布溶液１５を実施例１と同様にして基材に塗布し、基材上に皮膜を形成した。 Example 15
In the above formula (AI-26), 0.28 g of the compound (2) having an average value of n10 of 45 and 0.54 g of tetraethoxysilane were dissolved in 2.01 g of isopropanol and stirred at room temperature for 20 minutes. To the obtained solution, 0.0011 g of acetic acid as a catalyst and 0.18 g of water were added dropwise, and then stirred at room temperature for 4 hours to prepare a sample solution. The sample solution was diluted with 84.90 g of 2-ethoxyethyl acetate to obtain a coating solution 15. The coating solution 15 was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
　実施例１６
　酢酸２－エトキシエチル８４．９０ｇに代えて、酢酸２－メトキシ－１－メチルエチル８４．３９ｇを用いて塗布溶液１６を作製したこと以外は、実施例１５と同様にして基材上に皮膜を形成した。 Example 16
A coating was formed on the substrate in the same manner as in Example 15 except that 84.39 g of 2-methoxy-1-methylethyl acetate was used instead of 84.90 g of 2-ethoxyethyl acetate. Formed.
　比較例１
　上記の式（Ａ－Ｉ－２６）におけるｎ１０の平均値が２４である化合物（１）０．２９ｇ、テトラエトキシシラン０．７１ｇを、イソプロパノール２．１３ｇに溶解させ、室温で２０分撹拌した。得られた溶液に触媒としての酢酸０．１７ｇと水０．０２ｇを滴下した後、室温で４時間撹拌して試料溶液を作製した。前記試料溶液を、酢酸２－ブトキシエチル７１．４４ｇで希釈し、塗布溶液ａとした。塗布溶液ａを実施例１と同様にして基材に塗布し、基材上に皮膜を形成した。 Comparative Example 1
In the above formula (AI-26), 0.29 g of the compound (1) having an average value of n10 of 24 and 0.71 g of tetraethoxysilane were dissolved in 2.13 g of isopropanol and stirred at room temperature for 20 minutes. After 0.17 g of acetic acid as a catalyst and 0.02 g of water were added dropwise to the obtained solution, the sample solution was stirred for 4 hours at room temperature. The sample solution was diluted with 71.44 g of 2-butoxyethyl acetate to obtain a coating solution a. The coating solution a was applied to the substrate in the same manner as in Example 1 to form a film on the substrate.
　比較例２
　試料溶液を１－オクタノール６２．６２ｇで希釈して塗布溶液ｂを作製したこと以外は比較例１と同様にして、基材上に皮膜を形成した。 Comparative Example 2
A film was formed on the substrate in the same manner as in Comparative Example 1 except that the coating solution b was prepared by diluting the sample solution with 1-octanol 62.62 g.
　比較例３
　試料溶液をイソプロパノール５９．３６ｇで希釈して塗布溶液ｃを作製したこと以外は比較例１と同様にして基材上に皮膜を形成した。 Comparative Example 3
A film was formed on the substrate in the same manner as in Comparative Example 1 except that the coating solution c was prepared by diluting the sample solution with 59.36 g of isopropanol.
　結果を表６－１、表６－２及び表７に示す。また、実施例及び比較例で用いた溶媒の物性を表８に示す。 The results are shown in Table 6-1, Table 6-2 and Table 7. In addition, Table 8 shows the physical properties of the solvents used in Examples and Comparative Examples.
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
　２０℃における蒸気圧が０．０３２ｋＰａ以上１０ｋＰａ以下、かつｓｐ値が１１（ｃａｌ／ｃｍ3）1/2以下である溶媒（ｃ２）が、組成物中５質量％以上混合されている組成物から形成された実施例１～１６の皮膜は、温水試験後の水滴の滑落性が良好である。これに対して、溶媒（ｃ２）が混合されていない組成物から形成された比較例１～３の皮膜は、温水試験後の滑落性が悪い結果となった。 From a composition in which a solvent (c2) having a vapor pressure at 20 ° C. of 0.032 kPa to 10 kPa and an sp value of 11 (cal / cm 3 ) 1/2 or less is mixed in an amount of 5% by mass or more in the composition. The formed films of Examples 1 to 16 have good sliding properties of water droplets after the hot water test. On the other hand, the films of Comparative Examples 1 to 3 formed from the composition in which the solvent (c2) was not mixed had poor sliding properties after the hot water test.
　本発明の混合組成物から得られる皮膜は、撥水性、耐摩耗性、耐硫酸性及び耐温水性に優れている。そのため、タッチパネルディスプレイ等の表示装置、光学素子、半導体素子、建築材料、自動車部品、ナノインプリント技術等における基材として有用である。さらに、電車、自動車、船舶、航空機等の輸送機器におけるボディー、窓ガラス(フロントガラス、サイドガラス、リアガラス)、ミラー、バンパー等の物品として好適に用いられる。また、建築物外壁、テント、太陽光発電モジュール、遮音板、コンクリート、などの屋外用途にも用いることができる。漁網、虫取り網、水槽などにも用いることができる。更に、台所、風呂場、洗面台、鏡、トイレ周りの各部材の物品、シャンデリア、タイルなどの陶磁器、人工大理石、エアコン等の各種屋内設備にも利用可能である。また、工場内の治具や内壁、配管等の防汚処理としても用いることができる。ゴーグル、眼鏡、ヘルメット、パチンコ、繊維、傘、遊具、サッカーボールなどにも好適である。更に、食品用包材、化粧品用包材、ポットの内部、など、各種包材の付着防止剤としても用いることができる。 The film obtained from the mixed composition of the present invention is excellent in water repellency, abrasion resistance, sulfuric acid resistance and hot water resistance. Therefore, it is useful as a base material in display devices such as a touch panel display, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like. Furthermore, it is suitably used as an article such as a body, window glass (front glass, side glass, rear glass), mirror, bumper, etc. 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. Furthermore, 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.

Claims (9)

  1. 　少なくとも１つのトリアルキルシリル基含有分子鎖と、少なくとも１つの加水分解性基とがケイ素原子に結合している有機ケイ素化合物（ａ）と、
    　少なくとも１つの加水分解性基が金属原子に結合している金属化合物（ｂ）と、
    　２０℃における蒸気圧が０．０３２ｋＰａ以上１０ｋＰａ以下、かつｓｐ値が１１（ｃａｌ／ｃｍ3）1/2以下である溶媒（ｃ２）の混合組成物であって、
    　前記トリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
    　前記組成物中の有機ケイ素化合物（ａ）及び金属化合物（ｂ）の合計量が０．５質量％以上であり、
    　前記組成物中の前記溶媒（ｃ２）の量が５質量％以上であることを特徴とする混合組成物。     An organosilicon compound (a) in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom;
    A metal compound (b) having at least one hydrolyzable group bonded to a metal atom;
    A mixed composition of a solvent (c2) having a vapor pressure at 20 ° C. of 0.032 kPa to 10 kPa and an sp value of 11 (cal / cm 3 ) 1/2 or less,
    The hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom,
    The total amount of the organosilicon compound (a) and the metal compound (b) in the composition is 0.5% by mass or more,
    The amount of the said solvent (c2) in the said composition is 5 mass% or more, The mixed composition characterized by the above-mentioned.
  2. 　前記組成物中の前記溶媒（ｃ２）の量が３０質量％以上である請求項１に記載の組成物。 The composition according to claim 1, wherein the amount of the solvent (c2) in the composition is 30% by mass or more.
  3. 　２０℃における水の溶解度が２３１ｇ／Ｌ以上であり、かつｓｐ値が２０以下である溶媒（ｃ１）が混合されている請求項１または２に記載の組成物。 The composition according to claim 1 or 2, wherein a solvent (c1) having a water solubility at 20 ° C of 231 g / L or more and an sp value of 20 or less is mixed.
  4. 　ｓｐ値が１１（ｃａｌ／ｃｍ3）1/2超である溶媒（ｃ１）が混合されている請求項１または２に記載の組成物。 The composition according to claim 1 or 2, wherein a solvent (c1) having an sp value of more than 11 (cal / cm 3 ) 1/2 is mixed.
  5. 　イソプロパノール、エタノール、メタノール及びメチルエチルケトンよりなる群から選択される溶媒（ｃ１）の少なくとも１種が混合されている請求項１または２に記載の組成物。 The composition according to claim 1 or 2, wherein at least one solvent (c1) selected from the group consisting of isopropanol, ethanol, methanol and methyl ethyl ketone is mixed.
  6. 　組成物中の水分量が０．５質量％以下である請求項１～５のいずれかに記載の組成物。 The composition according to any one of claims 1 to 5, wherein the water content in the composition is 0.5% by mass or less.
  7. 　前記有機ケイ素化合物（ａ）が、下記式（Ａ１）で表される化合物である請求項１～６のいずれかに記載の組成物。
    Figure JPOXMLDOC01-appb-C000001
     　［前記式（Ａ１）中、Ｒa1はトリアルキルシリル基含有分子鎖を表し、
    　複数のＡa1は、それぞれ独立に、加水分解性基を表し、
    　Ｚa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表し、
    　Ｒa1及びＺa1におけるトリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
    　ｘは０または１である。］     The composition according to any one of claims 1 to 6, wherein the organosilicon compound (a) is a compound represented by the following formula (A1).
    Figure JPOXMLDOC01-appb-C000001
     [In the formula (A1), R a1 represents a trialkylsilyl group-containing molecular chain,
    Several A <a1> represents a hydrolysable group each independently,
    Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group,
    The hydrogen atom contained in the trialkylsilyl group in R a1 and Z a1 may be substituted with a fluorine atom,
    x is 0 or 1. ]
  8. 　前記金属化合物（ｂ）が下記式（Ｂ１）で表される化合物である請求項１～７のいずれかに記載の組成物。
    Figure JPOXMLDOC01-appb-C000002
     ［前記式（Ｂ１）中、ＭはＡｌ、Ｆｅ、Ｉｎ、Ｇｅ、Ｈｆ、Ｓｉ、Ｔｉ、Ｓｎ、Ｚｒ、または、Ｔａを表し、
    　Ｚb1は、シロキサン骨格含有基、炭化水素鎖含有基又は水素原子を表し、
    　複数のＡb1は、それぞれ独立に、加水分解性基を表し、
    　ｍは、金属原子に応じて、３～５の整数を表し、
    　ｒは０又は１である。］     The composition according to any one of claims 1 to 7, wherein the metal compound (b) is a compound represented by the following formula (B1).
    Figure JPOXMLDOC01-appb-C000002
     [In the formula (B1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta,
    Z b1 represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group or a hydrogen atom,
    Several A <b1> represents a hydrolysable group each independently,
    m represents an integer of 3 to 5, depending on the metal atom,
    r is 0 or 1; ]
  9. 　前記有機ケイ素化合物（ａ）が下記式（Ａ２）で表される化合物である請求項１～８のいずれかに記載の組成物。
    Figure JPOXMLDOC01-appb-C000003
     ［前記式（Ａ２）中、
    　複数のＡa1は、それぞれ独立に、加水分解性基を表し、
    　Ｚa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表し、該トリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
    　複数のＲs1は、それぞれ独立に、炭化水素基又はトリアルキルシリルオキシ基を表し、該炭化水素基又はトリアルキルシリルオキシ基に含まれる水素原子は、フッ素原子に置換されていてもよく、
    　複数のＲs2は、それぞれ独立に、炭素数１～１０のアルキル基を表し、
    　Ｚs1は、－Ｏ－又は２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2
    －は、－Ｏ－に置き換わっていてもよい。
    　Ｙs1は単結合又は－Ｓｉ（Ｒs2）2－Ｌs1－を表し、該Ｌs1は、２価の炭化水素基を表
    し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。
    　ｎ１は、１以上の整数を表し、
    　ｘは０または１である。］     The composition according to any one of claims 1 to 8, wherein the organosilicon compound (a) is a compound represented by the following formula (A2).
    Figure JPOXMLDOC01-appb-C000003
     [In the formula (A2),
    Several A <a1> represents a hydrolysable group each independently,
    Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group, and a hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom,
    A plurality of R s1 each independently represents a hydrocarbon group or a trialkylsilyloxy group, and a hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group may be substituted with a fluorine atom,
    A plurality of R s2 each independently represents an alkyl group having 1 to 10 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 —, the L s1 represents a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group is -O- may be substituted.
    n1 represents an integer of 1 or more,
    x is 0 or 1. ]
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