WO2019189791A1 - Composition mixte - Google Patents

Composition mixte 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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English (en)
Japanese (ja)
Inventor
彩香 櫻井
真芳 ▲徳▼田
泰治 島崎
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住友化学株式会社
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Priority to CN201980022412.6A priority Critical patent/CN111918927A/zh
Priority to KR1020207031030A priority patent/KR20200138780A/ko
Publication of WO2019189791A1 publication Critical patent/WO2019189791A1/fr

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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

La présente invention vise à pourvoir à une composition qui est apte à former un film présentant une excellente résistance à l'eau chaude. À cet effet, une composition mixte selon la présente invention est constituée d'un composé d'organosilicium (a) dans lequel au moins une chaîne moléculaire contenant un groupe trialkylsilyle et au moins un groupe hydrolysable sont liés à un atome de silicium, d'un composé métallique (b) dans lequel au moins un groupe hydrolysable est lié à un atome de métal, et d'un solvant (c2) dans lequel la pression de vapeur à 20 °C est comprise entre 0,032 kPa et 10 kPa et la valeur sp est inférieure ou égale à 11 (cal/cm3)1/2. La composition est caractérisée en ce que les atomes d'hydrogène inclus dans le groupe trialkylsilyle peuvent être substitués par des atomes de fluor, la quantité totale du composé organosilicium (a) et du composé métallique (b) dans la composition sont de 0,5 % en masse au minimum, et la quantité de solvant (c2) dans la composition est de 5 % en masse au minimum.
PCT/JP2019/014073 2018-03-30 2019-03-29 Composition mixte WO2019189791A1 (fr)

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