WO2020195629A1 - Composition et film - Google Patents

Composition et film Download PDF

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Publication number
WO2020195629A1
WO2020195629A1 PCT/JP2020/009079 JP2020009079W WO2020195629A1 WO 2020195629 A1 WO2020195629 A1 WO 2020195629A1 JP 2020009079 W JP2020009079 W JP 2020009079W WO 2020195629 A1 WO2020195629 A1 WO 2020195629A1
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Prior art keywords
group
hydrocarbon chain
acid
boiling point
compound
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PCT/JP2020/009079
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English (en)
Japanese (ja)
Inventor
みちる 上原
泰治 島崎
知典 宮本
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN202080024239.6A priority Critical patent/CN113631636A/zh
Priority to KR1020217023712A priority patent/KR20210144662A/ko
Publication of WO2020195629A1 publication Critical patent/WO2020195629A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • 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
    • 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
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a composition capable of forming a water- and oil-repellent film on various substrates.
  • the surface of a base material such as glass has good water and oil repellency.
  • it is required not only to prevent the adhesion of the droplets to the surface of the substrate, but also to facilitate the removal of the adhered droplets.
  • Patent Document 1 discloses an example in which an organic silane and a metal alkoxide are mixed at a predetermined ratio, and a solution containing an organic solvent, water, and a catalyst having a vapor pressure higher than that of water is spin-coated on a glass substrate.
  • Patent Document 2 discloses that a water repellent containing an amino-modified polysiloxane, an acid, and an activator is further applied by hand spraying a water repellent for glass containing an aminosilane.
  • Patent Document 3 discloses that a polishing composition for automobiles containing amino-modified dimethylpolysiloxane, alcohols, and water is applied by spraying.
  • Japanese Unexamined Patent Publication No. 2013-213181 Japanese Unexamined Patent Publication No. 2009-173491 JP-A-2009-40936 Japanese Unexamined Patent Publication No. 2017-202008
  • Patent Document 1 needs to use a coating device for spin coating
  • Patent Documents 2 and 3 need to use a coating device for spray coating, which is inferior in convenience.
  • Patent Document 4 discloses a composition containing an organic silicon compound having an alkyl group having 6 to 20 carbon atoms and a hydrolyzable group, a high boiling point solvent, and a low boiling point solvent, and this composition is a group. It is stated that the material can be hand-painted. However, a highly convenient coating operation such as hand coating can be performed regardless of the work place, and for example, it may be performed outdoors under the scorching sun. However, it has been found that when the composition of Patent Document 4 is applied under the scorching sun, the angle at which the water dropped on the coating film starts to slide (sliding angle) becomes large.
  • An object of the present invention is to provide a composition that can be applied by hand and that can maintain a small sliding angle even when applied under the scorching sun.
  • a hydrocarbon chain-containing group (AL6 to 20), which is an alkyl group having 6 to 20 carbon atoms in which a part of the methylene group may be replaced with an oxygen atom, and at least one hydrolyzable group are silicon atoms.
  • a high boiling point solvent (C2) that satisfies at least one of a vapor pressure at 20 ° C. of 1000 Pa or less and a boiling point of 120 ° C. or higher.
  • a mixed composition of a weak acid (E) having a pKa of 1 or more and 5 or less [2] The composition according to [1], wherein the organosilicon compound (A) is represented by the following formula (AI).
  • R a1 represents the hydrocarbon chain-containing group (AL6 to 20), and a plurality of A a1 independently represent the hydrolyzable group.
  • Z a1 represents a hydrocarbon chain-containing group (HC) or a hydrolyzable group, and when Z a1 is a hydrocarbon chain-containing group (HC), R a1 and Z a1 are the same but different.
  • Z a1 and A a 1 may be the same or different.
  • R a1 and Z a1 may be the same or different among a plurality of formulas (AI).
  • At least one hydrolyzable group is bonded to a metal atom.
  • a metal compound (B) in which a hydrocarbon chain-containing group (HC1 to 5), which is a hydrocarbon group having 1 to 5 carbon atoms in which a part of the methylene group may be replaced with an oxygen atom, may be bonded to the metal atom.
  • HC1 to 5 hydrocarbon chain-containing group
  • HC1 to 5 hydrocarbon group having 1 to 5 carbon atoms in which a part of the methylene group may be replaced with an oxygen atom
  • BI The composition according to [3], wherein the metal compound (B) is represented by the following formula (BI).
  • M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta.
  • n represents 0 or 1
  • m represents an integer of 1 or more.
  • the sum of n and m is equal to the valence of the metal M.
  • R b1 represents the hydrocarbon chain-containing group (HC1 to 5).
  • a b1 represents the hydrolyzable group, and when A b1 is plural, a plurality of A b1, respectively, may be the same or different.
  • [5] The composition according to [3] or [4], wherein the molar ratio of the metal compound (B) to the organosilicon compound (A) is 0.1 times or more and 48 times or less.
  • a water- and oil-repellent film can be formed by hand coating under the scorching sun.
  • a hydrocarbon chain-containing group (AL6 to 20), which is an alkyl group having 6 to 20 carbon atoms in which a part of the methylene group (meaning -CH 2- ; hereinafter the same) may be replaced with an oxygen atom, and at least 1 Organosilicon compound (A), in which one hydrophilic group is bonded to a silicon atom,
  • a low boiling point solvent (C1) having a vapor pressure of more than 1000 Pa and a boiling point of less than 120 ° C. at 20 ° C.
  • a high boiling point solvent (C2) that satisfies at least one of a vapor pressure at 20 ° C. of 1000 Pa or less and a boiling point of 120 ° C. or higher.
  • a mixed composition of a weak acid (E) having a pKa of 1 or more and 5 or less may be referred to as a water-repellent / oil-repellent film-forming composition.
  • the mixed composition of the organosilicon compound (A), the low boiling point solvent (C1), the high boiling point solvent (C2), and the weak acid (E) can be hand-coated on the base material under the scorching sun, and the obtained film is Has excellent water and oil repellency.
  • the mixed composition is a composition in which an organosilicon compound (A), a low boiling point solvent (C1), a high boiling point solvent (C2), and a weak acid (E) are mixed, and these (A) and (C1) are mixed.
  • This mixed composition and the mixed composition described later also include those whose reaction has proceeded after mixing, for example, during storage.
  • a plurality of types of hydrocarbon chain-containing groups in which the methylene group may be replaced with an oxygen atom including the hydrocarbon chain-containing group (AL6 to 20), will be described.
  • a hydrocarbon chain-containing group will be described using an example of an oxygen-unsubstituted type, but in any of the descriptions, the methylene group can be replaced with an oxygen atom unless otherwise specified.
  • Organosilicon compound (A) As described above, the organosilicon compound (A) is a hydrocarbon chain-containing group (AL6 to 20) which is an alkyl group having 6 to 20 carbon atoms in which a part of the methylene group may be replaced with an oxygen atom. ) Are combined. Since the alkyl group has a hydrocarbon chain and a group in which a part of the alkyl group is replaced with an oxygen atom also has a hydrocarbon chain in the remaining part, the alkyl group and a group in which a part thereof is replaced with an oxygen atom Is classified as a hydrocarbon chain-containing group.
  • the hydrocarbon chain-containing group (AL6 to 20) imparts water and oil repellency to the obtained film interface (surface).
  • the coefficient of friction between the droplets (water droplets, oil droplets, etc.) and the film becomes small, and the droplets can move easily.
  • the hydrocarbon chain-containing group (AL6 to 20) the methylene group adjacent to the Si atom is not replaced with the oxygen atom, and two consecutive methylene groups are not replaced with the oxygen atom at the same time.
  • the organosilicon compound (A) may be used alone or in combination of two or more.
  • the hydrocarbon chain-containing group (AL6 to 20) may be a branched chain or a straight chain.
  • the hydrocarbon chain-containing group (AL6 to 20) preferably has 7 or more and 17 or less carbon atoms, and more preferably 8 or more and 15 or less carbon atoms.
  • the carbon number of the hydrocarbon chain-containing group (AL6 to 20) is the carbon number before the methylene group is replaced with an oxygen atom. It shall mean the number of carbon atoms of the alkylene group.
  • Alkyl groups having 6 to 20 carbon atoms include, for example, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group.
  • a group, a nonadecyl group, an icosyl group and the like are included.
  • the group in which a part of the methylene group of the alkyl group having 6 to 20 carbon atoms is replaced with the oxygen atom includes a group having a (poly) ethylene glycol unit, a group having a (poly) propylene glycol unit, and the like.
  • hydrocarbon chain-containing groups (HC) having an arbitrary number of carbon atoms may be bonded to the silicon atom of the organosilicon compound (A).
  • the hydrocarbon chain-containing group (HC) is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group, more preferably a saturated aliphatic hydrocarbon chain-containing group, and preferably an alkyl group. Even more preferable.
  • a part of the methylene group may be replaced with an oxygen atom.
  • the methylene group adjacent to the Si atom is not replaced with an oxygen atom, and two consecutive methylene groups are not replaced with an oxygen atom at the same time.
  • the hydrocarbon chain-containing group (HC) in which a part of the methylene group is replaced with an oxygen atom include a group having a (poly) ethylene glycol unit, a group having a (poly) propylene glycol unit, and the like.
  • the hydrocarbon chain-containing group (HC) preferably has 1 or more carbon atoms and 20 or less carbon atoms.
  • the carbon number of the hydrocarbon chain-containing group (HC) is the carbon number of the alkylene group before the methylene group is replaced with the oxygen atom.
  • hydrocarbon chain-containing group (HC) preferably a hydrocarbon chain-containing group (HC) having 6 to 20 carbon atoms in which a part of the methylene group may be replaced with an oxygen atom, and more preferably a part of the methylene group.
  • HC hydrocarbon chain-containing group
  • examples thereof include an alkyl group having 6 to 20 carbon atoms which may be replaced with an oxygen atom (that is, a group similar to the hydrocarbon chain-containing group (AL6 to 20)).
  • the hydrocarbon chain-containing group (HC) is preferably a hydrocarbon group in which a part of the methylene group may be replaced with an oxygen atom, and the maximum chain length (also referred to as a main chain) of the hydrocarbon chain portion.
  • HCS hydrocarbon chain-containing group
  • AL6 to 20 the maximum chain length of the hydrocarbon chain portion.
  • ALS hydrocarbon chain-containing group
  • the methylene group adjacent to the Si atom is not replaced by the oxygen atom, and two consecutive methylene groups are not replaced by the oxygen atom at the same time.
  • the maximum chain length is compared before the methylene group is replaced with an oxygen atom.
  • hydrocarbon chain-containing group (HCS) or (ALS) In order to make the maximum chain length of the hydrocarbon chain-containing group (HCS) or (ALS) shorter than the maximum chain length of the hydrocarbon chain-containing group (AL6 to 20), the hydrocarbon chain-containing group (HCS) or The number of carbon atoms of the hydrocarbon group or alkyl group forming (ALS) may be smaller than the number of carbon atoms (6 to 20) of the alkyl group forming the hydrocarbon chain-containing group (AL6 to 20). The number of carbon atoms of the group or alkyl group may be 1 to 5. Hydrocarbon chain-containing groups (HCS) having 1 to 5 carbon atoms are hereinafter referred to as hydrocarbon chain-containing groups (HC1 to 5), and hydrocarbon chain-containing groups (ALS) having 1 to 5 carbon atoms. Those having a value of ⁇ 5 are hereinafter referred to as hydrocarbon chain-containing groups (AL1 to 5).
  • the hydrocarbon chain-containing group (HCS) is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group in which a part of the methylene group may be replaced with an oxygen atom, and a part of the methylene group is an oxygen atom. It is more preferable that it is a saturated aliphatic hydrocarbon chain-containing group which may be replaced with, and an alkyl group (that is, a hydrocarbon chain-containing group (ALS)) in which a part of the methylene group may be replaced with an oxygen atom is more preferable. More preferred. As the saturated aliphatic hydrocarbon chain-containing group or the hydrocarbon chain-containing group (ALS), an oxygen-unsubstituted saturated aliphatic hydrocarbon group is more preferable.
  • Saturated aliphatic hydrocarbon groups include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like.
  • the hydrocarbon chain-containing groups (HC1 to 5) and (AL1 to 5) have more preferably 1 or more and 3 or less carbon atoms.
  • hydrocarbon chains of the hydrocarbon chain-containing groups may be straight chains or branched chains.
  • hydrocarbon chain-containing group (AL6 to 20) as a hydrocarbon chain-containing group (HC) is bonded to a silicon atom of the organic silicon compound (A)
  • a plurality of hydrocarbon chain-containing groups (AL6 to 20) are bonded to the silicon atom. 20) will be combined.
  • the two hydrocarbon chain-containing groups (AL6-20) attached to the silicon atom may be the same or different.
  • hydrocarbon chain-containing group (HCS) as a hydrocarbon chain-containing group (HC) is bonded to the silicon atom of the organic silicon compound (A), the silicon atom has two types of hydrocarbon chains having different longest chain lengths.
  • the containing groups (AL6 to 20) and (HCS) will be bonded.
  • the number of hydrocarbon chain-containing groups (HC) bonded to the silicon atom is any of 0, 1, and 2, preferably 0, 1, and more preferably 0.
  • the hydrolyzable group bonded to the silicon atom of the organic silicon compound (A) may be a group that gives a hydroxy group (silanol group) by hydrolysis, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or the like.
  • Alkoxy group having 1 to 4 carbon atoms; hydroxy group; acetoxy group; chlorine atom; isocyanate group; and the like can be preferably mentioned. Of these, an alkoxy group having 1 to 4 carbon atoms is preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.
  • the number of hydrolyzable groups bonded to the silicon atom is usually 1 or more, preferably 2 or more, and usually 3 or less. Most preferably, the number of hydrolyzable groups bonded to the silicon atom is 3.
  • the organosilicon compound (A) is preferably a compound represented by the following formula (AI).
  • R a1 represents the hydrocarbon chain-containing group (AL6 to 20), and a plurality of A a1 independently represent the hydrolyzable group.
  • Z a1 represents the hydrocarbon chain-containing group (HC) or a hydrolyzable group, and when Z a1 is a hydrocarbon chain-containing group (HC), R a1 and Z a 1 are different even if they are the same.
  • Z a1 and A a 1 may be the same or different.
  • R a1 and Z a1 may be the same or different among a plurality of formulas (AI).
  • Za1 is preferably the hydrocarbon chain-containing group (HCS) or a hydrolyzable group, and more preferably a hydrolyzable group.
  • Z a1 is a hydrocarbon chain-containing group (HCS)
  • the Z a1 is more preferably a hydrocarbon chain-containing group (ALS), and more preferably a hydrocarbon chain-containing group (AL1 to 5). More preferred.
  • the organic silicon compound (A) is a compound having one hydrocarbon chain-containing group (AL6 to 20) and three hydrolyzable groups; one carbon number chain-containing group (AL6 to 20) and a hydrocarbon chain.
  • a compound having one containing group (HCS) and two hydrolyzable groups; and the like can be preferably mentioned.
  • a compound having one hydrocarbon chain-containing group (AL6 to 20) and three hydrolyzable groups has a group in which three hydrolyzable groups are bonded to a silicon atom.
  • the groups to which the three hydrolyzable groups are bonded to the silicon atom include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, tripropoxysilyl group and tributoxysilyl group; trihydroxysilyl group; triacetoxysilyl group. Groups; trichlorosilyl groups; triisocyandiasilyl groups; and the like.
  • Compounds having one hydrocarbon chain-containing group (AL6 to 20), one hydrocarbon chain-containing group (HCS), and two hydrolyzable groups are one hydrocarbon chain-containing group (HCS) and two.
  • One hydrolyzable group has a group attached to a silicon atom.
  • Examples of the group in which one hydrocarbon chain-containing group (HCS) and two hydrolyzable groups are bonded to a silicon atom include a methyldimethoxysilyl group, an ethyldimethoxysilyl group, a methyldiethoxysilyl group and an ethyldiethoxysilyl group.
  • Alkyldialkoxysilyl groups such as methyldipropoxysilyl groups; and the like.
  • the compound having one hydrocarbon chain-containing group (AL6 to 20) and three hydrolyzable groups include alkyltrimethoxysilane having an alkyl group having 6 to 20 carbon atoms and 6 to 6 carbon atoms.
  • Alkyl trialkoxysilane having an alkyl group having 6 to 20 carbon atoms such as alkyl triethoxysilane having an alkyl group of 20; Alkyl trihydroxysilane having an alkyl group having 6 to 20 carbon atoms; Alkyl group having 6 to 20 carbon atoms Alkyltriacetoxysilane having an alkyl group having 6 to 20 carbon atoms; alkyltrichlorosilane having an alkyl group having 6 to 20 carbon atoms; alkyltriisocyanatesilane having an alkyl group having 6 to 20 carbon atoms; and the like.
  • the number of carbon atoms is 6 to 20.
  • Alkylmethyldimethoxysilane having an alkyl group of 6 to 20 alkylmethyldiethoxysilane having an alkyl group having 6 to 20 carbon atoms; alkylmethyldihydroxysilane having an alkyl group having 6 to 20 carbon atoms; Examples thereof include alkylmethyldiacetoxysilane having an alkyl group of 6 to 20; alkylmethyldichlorosilane having an alkyl group having 6 to 20 carbon atoms; alkylmethyldiisocyanatesilane having an alkyl group having 6 to 20 carbon atoms; and the like.
  • a compound having one alkyl group having 6 to 20 carbon atoms and three hydrolyzable groups is preferable, and an alkyltrialkoxysilane having an alkyl group having 6 to 20 carbon atoms is more preferable.
  • the amount of the organosilicon compound (A) is preferably, for example, 0.001 to 2.0% by mass, more preferably 0, when the entire composition for forming a water-repellent / oil-repellent film is 100% by mass. It is .005 to 1.6% by mass, more preferably 0.01 to 1.2% by mass.
  • the amount of the organic silicon compound (A) is preferably 0.0015 to 3.0% by mass, more preferably 0.0015 to 3.0% by mass, based on 100% by mass of the total of the low boiling solvent (C1) and the high boiling solvent (C2). Is 0.055 to 2.4% by mass, and even more preferably 0.075 to 1.7% by mass.
  • the amount of the organosilicon compound (A) can be adjusted at the time of preparing the composition.
  • the amount of the organosilicon compound (A) may be calculated from the analysis result of the composition.
  • the range of the amount, mass ratio or molar ratio of each component is described in the present specification, the range can be adjusted at the time of preparing the composition in the same manner as described above.
  • the organosilicon compound (A) is preferably used in combination with a predetermined metal compound (B), if necessary.
  • the metal compound (B) is a compound in which at least one hydrolyzable group is bonded to a metal atom, and a hydrocarbon chain-containing group (HC1 to 5) may be bonded to the metal atom.
  • HC1 to 5 a hydrocarbon chain-containing group
  • the metal atom of the metal compound (B) may be any metal atom that can be bonded to an alkoxy group to form a metal alkoxide, and the metal in this case also includes semi-metals such as Si and Ge.
  • Specific examples of the metal atom of the metal compound (B) include trivalent metals such as Al, Fe, and In; tetravalent metals such as Ge, Hf, Si, Ti, Sn, and Zr; and pentavalent metals such as Ta. , Etc., preferably a trivalent metal such as Al; a tetravalent metal such as Si, Ti, Zr, Sn;, more preferably Al, Si, Ti, Zr, and further preferably Si. ..
  • the alkoxides of these metal atoms are easy to liquefy, and it is easy to improve the uniformity of the distribution of the following structure (b) that can function as a spacer in the film.
  • hydrolyzable group of the metal compound (B) examples include those similar to the hydrolyzable group of the organosilicon compound (A), preferably an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 2 carbon atoms. Groups are more preferred. Further, the hydrolyzable groups of the organosilicon compound (A) and the metal compound (B) may be the same or different. Further, the hydrolyzable groups of the organosilicon compound (A) and the metal compound (B) are preferably alkoxy groups having 1 to 4 carbon atoms. In the metal compound (B), the number of hydrolyzable groups is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 4 or less. Most preferably, the number of hydrolyzable groups is 4.
  • the hydrocarbon chain-containing group (HC1 to 5) of the metal compound (B) means a hydrocarbon group having 1 to 5 carbon atoms in which a part of the methylene group may be replaced with an oxygen atom.
  • the hydrocarbon group having 1 to 5 carbon atoms is preferably a chain aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, and more preferably an alkyl group.
  • the chain aliphatic hydrocarbon group may be a branched chain or a straight chain.
  • the hydrocarbon chain-containing group (HC1 to 5) preferably has 1 or more and 3 or less carbon atoms.
  • the carbon number of the hydrocarbon chain-containing group (HC1 to 5) is the carbon number before the methylene group is replaced with an oxygen atom. It shall mean the number of carbon atoms of the alkylene group.
  • Alkyl groups as hydrocarbon chain-containing groups include, for example, methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, 2-methylpropyl group, tert-butyl group. , N-pentyl group, 3-methylbutyl group and the like.
  • Examples of the group in which a part of the methylene group of the alkyl group having 1 to 5 carbon atoms is replaced with the oxygen atom include a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group and the like.
  • the alkenyl group as the hydrocarbon chain-containing group includes, for example, a vinyl group, an allyl group, a butenyl group, a butandienyl group and the like.
  • the number of hydrocarbon chain-containing groups (HC1 to 5) in the metal compound (B) is preferably 1 or less, and particularly preferably 0.
  • the metal compound (B) is preferably a compound represented by the following formula (BI).
  • M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta.
  • n represents 0 or 1
  • m represents an integer of 1 or more.
  • the sum of n and m is equal to the valence of the metal M.
  • R b1 represents the hydrocarbon chain-containing group (HC1 to 5).
  • a b1 represents the hydrolyzable group, and when A b1 is plural, a plurality of A b1, respectively, may be the same or different.
  • n is preferably 0.
  • the hydrolyzable group represented by A b1 may be the same as or different from the hydrolyzable group of the organosilicon compound (A).
  • the valence of the metal M ie, the sum of n and m
  • M is 3 when M is Al, Fe, or In, and 4 when M is Ge, Hf, Si, Ti, Sn, or Zr.
  • M is 5 when it is Ta.
  • a compound having only a hydrolyzable group As the metal compound (B), a compound having only a hydrolyzable group; a compound having one hydrocarbon chain-containing group (HC1 to 5) and a plurality of hydrolyzable groups; and the like can be preferably mentioned.
  • the compound having only a hydrolyzable group include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; trialkoxyaluminum such as triethoxyaluminum, tripropoxyaluminum, and tributoxyaluminum; triethoxy.
  • Trialkoxy iron such as iron; trialkoxy indium such as trimethoxyindium, triethoxyindium, tripropoxyindium, tributoxyinum; tetraalkoxygermanium such as tetramethoxygermanium, tetraethoxygermanium, tetrapropoxygermanium, tetrabutoxygermanium; tetra Tetraalkoxyhafnium such as methoxyhafnium, tetraethoxyhafnium, tetrapropoxyhafnium, tetrabutoxyhafnium; tetraalkoxytitanium such as tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium; tetramethoxytin, tetraethoxytin, tetra Tetraalkoxytin such as propoxytin and tetra
  • Examples of the compound having a hydrocarbon chain-containing group (HC1 to 5) and a hydrolyzable group include alkyltrialkoxy such as methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and methyltripropoxysilane.
  • alkyltrialkoxy such as methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and methyltripropoxysilane.
  • Silanes alkenyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; and the like.
  • the molar ratio of the metal compound (B) to the organosilicon compound (A) is 0.1 times or more and 48 times or less. preferable.
  • the lower limit of the molar ratio is more preferably 0.2, even more preferably 0.5, particularly preferably 0.8, and most preferably 1.0.
  • the upper limit of the molar ratio is preferably 44 or less, more preferably 40 or less, particularly preferably 36 or less, and most preferably 20 or less, or 10 or less.
  • the total amount of the organic silicon compound (A) and the metal compound (B) is preferably 0.005% by mass or more, more preferably 0.005% by mass or more, based on 100% by mass of the total of the low boiling point solvent (C1) and the high boiling point solvent (C2). Is 0.025% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.25% by mass or more, and particularly preferably 1.0% by mass or more.
  • the total amount of the organosilicon compound (A) and the metal compound (B) is, for example, 30% by mass or less, preferably 30% by mass or less, based on 100% by mass of the total of the low boiling point solvent (C1) and the high boiling point solvent (C2). Is 20% by mass or less, more preferably 10% by mass or less.
  • one alkyl group having 8 or more and 12 or less carbon atoms and three hydrolyzable groups are bonded to silicon atoms as the organic silicon compound (A).
  • the metal compound (B) a compound in which four hydrolyzable groups are bonded to a metal atom (particularly a silicon atom) is used, and the metal compound (B) and the organic silicon compound (A) are used.
  • the mass ratio (metal compound (B) / organic silicon compound (A)) is, for example, 0.3 or more, preferably 0.5 or more, more preferably 0.7 or more, and for example, 36 or less, preferably 10. It is particularly preferable that the composition is as follows. By adjusting the structure and mass ratio of the organosilicon compound (A) and the metal compound (B) in this way, it is possible to achieve both the hardness of the obtained film and the water and oil repellency.
  • the low boiling point solvent (C1) in the water-repellent / oil-repellent film composition volatilizes rapidly, so that the film-forming property of the composition can be improved.
  • the low boiling point solvent means a solvent having a vapor pressure of more than 1000 Pa at 20 ° C. and a boiling point of less than 120 ° C.
  • the melting point of the low boiling point solvent is, for example, 15 ° C. or lower, preferably 0 ° C. or lower.
  • Examples of such a low boiling point solvent (C1) include alcohol-based solvents, ketone-based solvents, ether-based solvents, and alicyclic hydrocarbon-based solvents, and alcohol-based solvents, ketone-based solvents, and ether-based solvents are particularly preferable.
  • Alcohol-based solvents are most preferred.
  • the alcohol solvent is, for example, methanol, ethanol, 1-propanol, isopropyl alcohol, 2,2,2-trifluoroethanol, 2-butanol, isobutyl alcohol and the like.
  • the ketone solvent is, for example, acetone, ethyl methyl ketone and the like.
  • ether solvent examples include diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether and the like.
  • alicyclic hydrocarbon solvent examples include hexane.
  • the vapor pressure of the low boiling point solvent (C1) at 20 ° C. is preferably 2000 Pa or more, more preferably 3000 Pa or more, and the upper limit is not particularly limited, but is, for example, 13000 Pa.
  • the organosilicon compound (A) is preferably, for example, 0.001 to 3.5% by mass, more preferably 0.005 to 3.0% by mass, based on 100% by mass of the low boiling point solvent (C1). It is mass%.
  • the metal compound (B) is preferably, for example, 0.001 to 3.5% by mass, more preferably 0.005 to 3.0% by mass, based on 100% by mass of the low boiling point solvent (C1). %.
  • High boiling point solvent (C2) By using a high boiling point solvent (C2) in the composition for a water-repellent / oil-repellent film, it becomes possible to apply it by hand under the scorching sun, and the obtained film becomes excellent in water-repellent / oil-repellent property.
  • the high boiling point solvent means a solvent satisfying at least one of a vapor pressure at 20 ° C. of 1000 Pa or less and a boiling point of 120 ° C. or higher.
  • the melting point of the high boiling point solvent is, for example, 30 ° C. or lower, preferably 0 ° C. or lower.
  • Examples of the high boiling point solvent (C2) include aromatic hydrocarbons having substituents such as m-xylene and chlorobenzene; monools having 4 or more carbon atoms such as 1-butanol, 2-ethyl-1-hexanol and cyclohexanol. Classes; polyols such as ethylene glycol, 1,3-butanediol, 1,4-butanediol, glycerin; condensed ethers of the above-mentioned polyols such as diethylene glycol and polyethylene glycol (hereinafter, may be referred to as "condensed ether").
  • Mono or polyether products of the polyols or condensed ethers such as ethylene glycol monohexyl ether, ethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (hereinafter, may be referred to as "polypoly ether”); ethylene glycol.
  • Esterates of the polyols or condensed ethers such as diacetate and propylene carbonate (hereinafter sometimes referred to as “polyester esters”); esterified products of the monools such as n-butyl acetate (hereinafter “monoesters").
  • Aromatic ester compounds such as acetophenone; nitrogen-containing solvents such as aniline and N-ethylmorpholin may be mentioned.
  • These high boiling point solvents (C2) may be used alone or in combination of two or more.
  • the preferred high boiling point solvent (C2) is monools having 4 or more carbon atoms, polyols, condensed ether, polyol ether and the like, and more preferably polyols.
  • Table 1 shows the boiling point, vapor pressure, and solubility parameters of the specific example of the high boiling point solvent (C2). In Table 1, isopropanol corresponding to the low boiling point solvent (C1) is also listed for reference.
  • the solubility parameter (SP value, solubility parameter) is preferably 8.0 (cal / cm 3 ) 1/2 or more.
  • the solubility parameter (SP value) is more preferably 12.0 (cal / cm 3 ) 1/2 or more, and further preferably 14.0 (cal / cm 3 ) 1/2 or more. ..
  • the solubility parameter is set to 12.0 (cal / cm 3 ) 1/2 or more, especially 14.0 (cal / cm 3 ) 1/2 or more, after hand-coating the water-repellent / oil-repellent film composition under the scorching sun.
  • the solubility parameter (SP value) is, for example, 18 (cal / cm 3 ) 1/2 or less.
  • the solubility parameter (SP value) is a value calculated by the method described in "RF Fedors, Polym. Eng. Sci., 14 [2], 147-154 (1974)".
  • the vapor pressure of the high boiling point solvent (C2) at 20 ° C. is preferably 800 Pa or less, more preferably 600 Pa or less, and the lower limit is not particularly limited, but is, for example, 5 Pa.
  • the boiling point of the high boiling point solvent (C2) is preferably 150 ° C. or higher, more preferably 170 ° C. or higher, and the upper limit is not particularly limited, but is, for example, 300 ° C.
  • the high boiling point solvent (C2) is preferably, for example, 0.01 to 15% by mass, more preferably 0.01 to 10% by mass, based on 100% by mass of the low boiling point solvent (C1). It is more preferably 0.05 to 5% by mass, and may be 3% by mass or less.
  • the high boiling point solvent (C2) is preferably, for example, 0.5 to 210000% by mass, more preferably 2.5 to 170000% by mass, still more, based on 100% by mass of the organosilicon compound (A). It is preferably 5.0 to 85,000% by mass. The lower limit may be 50% by mass, 70% by mass, 100% by mass, or the like.
  • the upper limit may be 20000% by mass, 15000% by mass, 10000% by mass, 5000% by mass, 3000% by mass, 1000% by mass, 500% by mass, or the like.
  • the high boiling point solvent (E) is preferably 1 to 10000% by mass, more preferably 5 to 5000% by mass, based on 100% by mass of the total of the organosilicon compound (A) and the metal compound (B). , More preferably 10 to 3000% by mass.
  • a solvent other than the low boiling point solvent (C1) and the high boiling point solvent (C2) may be mixed, if necessary. ..
  • the other solvent is, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, based on 100% by mass of the total of the low boiling solvent (C1) and the high boiling solvent (C2). , More preferably 5% by mass or less, particularly preferably 1% by mass or less, and may be 0% by mass.
  • Water (D) In the composition for water-repellent / oil-repellent film, water (D) may be mixed if necessary. When water (D) is mixed, the water and oil repellency properties when hand-applied under the scorching sun are further improved.
  • the water (D) may be water contained in the aqueous solution when a weak acid (E), a catalyst (F), etc., which will be described later, are used as the aqueous solution, or water added alone, but alone. It is preferably the water added in.
  • the ratio of the high boiling point solvent (C2) to 100% by mass of water (D) is preferably, for example, 0.01 to 30% by mass, more preferably 0.05 to 15% by mass, and even more preferably. It is 0.1 to 10% by mass, more preferably 0.5 to 7.0% by mass, and particularly preferably 0.9 to 6.0% by mass.
  • the ratio of the water (D) to 100% by mass of the organosilicon compound (A) is, for example, 30.0% by mass or more.
  • the above ratio is preferably 50% by mass or more, more preferably 100% by mass or more, still more preferably 1000% by mass or more, still more preferably 5000% by mass or more, and particularly preferably 10000% by mass or more.
  • the upper limit of the ratio (D / A) is not particularly limited, but is, for example, 80,000,000% by mass or less, more preferably 64,000,000% by mass or less, and further preferably 32000000% by mass or less.
  • the weak acid (E) is used in the composition for the water-repellent / oil-repellent film, excellent water-repellent / oil-repellent properties can be imparted to the coating film when hand-coated under the scorching sun.
  • the pKa of the weak acid (E) is preferably 4.3 or less, more preferably 4.0 or less, and even more preferably 3.5 or less.
  • the weak acid pKa is, for example, 1 or more.
  • the weak acid (E) has a plurality of pKa, the genus / non-genus of the range of pKa is determined based on the smallest pKa.
  • the weak acid (E) may be either an inorganic acid or an organic acid, and examples thereof include a carboxylic acid compound and a phosphoric acid compound.
  • the weak acid (E) may be used alone or in combination of two or more.
  • the carboxylic acid compound may be either a monovalent carboxylic acid compound or a polyvalent carboxylic acid compound (a carboxylic acid compound having two or more carboxy groups), but a polyvalent carboxylic acid compound is preferable.
  • the polyvalent carboxylic acid compound is oxalic acid in which two carboxy groups are directly bonded, or a carboxy group is bonded to both ends of a divalent hydrocarbon group, and the main chain of the hydrocarbon group ( The longest linear) has 1 to 15 carbon atoms (more preferably 1 to 5 carbon atoms, still more preferably 1 to 4 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon number.
  • the divalent hydrocarbon group may be linear or branched, may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • a hydroxy group or a carboxy group may be bonded to a carbon atom other than both ends of the hydrocarbon group.
  • the carboxylic acid compound (E) is more preferably oxalic acid, or at both ends of a saturated or unsaturated linear hydrocarbon group having 1 to 3 carbon atoms (particularly 1 or 2 carbon atoms). It is a dicarboxylic acid or a tricarboxylic acid to which a carboxy group is bonded.
  • the carboxylic acid compound (E) may be a polymer having at least one carboxy group in the molecule.
  • the polymer include a polymer containing a structural unit having a carboxy group in the side chain, and may contain a structural unit having two or more kinds of carboxy groups in the side chain.
  • the polymer having at least one carboxy group in the molecule include a (meth) acrylic polymer having a carboxy group, a polyester polymer having a carboxy group, and a polyolefin polymer having a carboxy group.
  • the carboxylic acid compound (E) preferably has a molecular weight of 1000 or less, and more preferably 500 or less.
  • the molecular weight is preferably 50 or more, and more preferably 80 or more.
  • carboxylic acid compound (E) a compound represented by the following formula (e1) is preferable.
  • R c1 and R c2 are independently single-bonded and may have a carboxy group, and are divalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms or carboxy groups. Represents a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have.
  • R c3 and R c4 each independently represent an alkyl group having 1 to 10 carbon atoms, which may have a carboxy group, or a hydrogen atom. q1 is 0 or 1.
  • the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R c1 and R c2 may be a straight chain, a branched chain, or a cyclic chain. Specific examples of R c1 and R c2 include alkanediyl groups such as a methylene group, an ethylene group, a propylene group and a butylene group. Examples of the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R c1 and R c2 include a phenylene group and the like.
  • the divalent aliphatic hydrocarbon group represented by R c1 and R c2 or the divalent aromatic hydrocarbon group may have a carboxy group.
  • R c1 is preferably a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be a single bond or may have a carboxy group, and R c1 is a single bond or a carboxy group.
  • a divalent linear aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have the above is more preferable.
  • R c2 is preferably a single bond.
  • the alkyl group having 1 to 10 carbon atoms represented by R c3 and R c4 may be a linear group, a branched chain, or a cyclic group, and specifically, methyl. Examples include a group, an ethyl group, a propyl group, a butyl group and the like.
  • R c3 is preferably a hydrogen atom.
  • R c4 is preferably a hydrogen atom.
  • the compound represented by the above formula (e1) is more preferably a compound represented by the following formula (e2).
  • p is an integer of 0 to 2.
  • the p is preferably 1.
  • the carboxylic acid compound may be one kind or a combination of two or more kinds.
  • the phosphoric acid compound may be one kind or a combination of two or more kinds.
  • the weak acid (E) is preferably 1 to 21% by mass, more preferably 1 to 15% by mass, and more preferably 1 to 15% by mass with respect to 100% by mass of the total of the organosilicon compound (A) and the metal compound (B). More preferably, it is 1.5 to 10.5% by mass.
  • Catalyst (F) In the water- and oil-repellent film-forming composition of the present invention, it is preferable to use the catalyst (F) generally used in the sol-gel method.
  • the catalyst (F) include a base catalyst, an organometallic catalyst, a strong acid having a pKa1 or less, and a strong acid having a pKa1 or less is preferable.
  • the strong acid include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic sulfonic acids such as methanesulfonic acid and toluenesulfonic acid.
  • the strong acid such as hydrochloric acid may be an aqueous solution. In the present invention, the water constituting the aqueous solution is contained in the water (D).
  • the catalyst (F) (particularly preferably hydrochloric acid) is preferably 0.01% by mass or more, more preferably 0% by mass, based on 100% by mass of the total of the organic silicon compound (A) and the metal compound (B). It is 03% by mass or more, preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and further preferably 0.2% by mass or less.
  • composition for forming a water- and oil-repellent film is an antioxidant, a rust preventive, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, as long as the effect of the present invention is not impaired.
  • Various additives such as biofouling inhibitors, deodorants, pigments, flame retardants, and antistatic agents may be mixed.
  • antioxidants examples include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, hindered amine-based antioxidants, and the like.
  • phenolic antioxidant examples include n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, 2, 2-thio-diethylene-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tri-ethylene glycol-bis- [3- (3-t-butyl-5-methyl) -4-Hydroxyphenyl) propionate], 3,9-bis [2- ⁇ 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ -1,1-dimethylethyl] -2, 4,8,10-Tetraoxaspiro [5.5] undecane, tetrakis ⁇ 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionic acid ⁇ pentaerythrityl ester, 2-t-but-
  • sulfur-based antioxidant examples include 3,3'-thiodipropionic acid di-n-dodecyl ester, 3,3'-thiodipropionic acid di-n-tetradecyl ester, and 3,3'-thiodipropion.
  • examples thereof include acid di-n-octadecyl ester and tetrakis (3-dodecylthiopropionic acid) pentaerythritol ester.
  • Examples of the phosphorus-based antioxidant include tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, and bis (2,6-di-).
  • hindered amine-based antioxidant examples include bis sebacate (2,2,6,6-tetramethyl-4-piperidyl) ester, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, and poly [ ⁇ 6. -(1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ - 1,6-hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ] and the like can be mentioned.
  • Examples of the rust preventive include alkanolamines such as triethanolamine; quaternary ammonium salts; alcanthiol; imidazolines, imidazoles, alkylimidazoline derivatives, benzimidazoles, 2-mercaptobenzimidazoles, benzotriazoles and other azoles; metavanazic acid.
  • alkanolamines such as triethanolamine; quaternary ammonium salts; alcanthiol; imidazolines, imidazoles, alkylimidazoline derivatives, benzimidazoles, 2-mercaptobenzimidazoles, benzotriazoles and other azoles; metavanazic acid.
  • Sodium bismuth citrate; phenol derivatives; aliphatic amines such as alkylamines and polyalkenylamines, aromatic amines, ethoxylated amines, cyanoalkylamines, cyclohexylamine benzoate, aliphatic
  • Amine compounds amides of the amine compounds and carboxylic acids; alkyl esters; pyrimidin; naphthenic acid; sulfonic acid complexes; nitrites such as calcium nitrite, sodium nitrite, dicyclohexylamine nitrite; polyalcohol, polyphenols, etc.
  • Examples of the ultraviolet absorber / light stabilizer include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl].
  • antifungal / antibacterial agent examples include 2- (4-thiazolyl) benzimidazole, sorbic acid, 1,2-benzisothiazolin-3one, sodium (2-pyridylthio-1-oxide), dehydroacetic acid, and 2-methyl.
  • bioadhesion inhibitor examples include tetramethylthiuram disulfide, bis (N, N-dimethyldithiocarbamic acid) zinc, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, and dichloro-N-((dimethylamino)).
  • deodorant examples include lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediaminepolyacetic acid, alkane-1,2-dicarboxylic acid, alken-1,2-dicarboxylic acid, and cycloalcan-1.
  • Acrylic polymers such as porous methacrylic acid polymer and porous acrylic acid polymer, porous divinylbenzene polymer, porous styrene-divinylbenzene-vinylpyridine polymer, aromatic polymer such as porous divinylbenzene-vinylpyridine polymer, and their co-weight.
  • examples thereof include polymers and polymers such as chitin, chitosan, activated charcoal, silica gel, active alumina, zeolite, and ceramics.
  • the pigment examples include carbon black, titanium oxide, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, perylene or perinone pigment, quinophthalone pigment, diketopyrrolopyrrole pigment, dioxazine pigment, disazo condensation pigment and the like.
  • examples thereof include benzimidazolone pigments.
  • Examples of the flame retardant include decabromobiphenyl, antimony trioxide, phosphorus-based flame retardant, aluminum hydroxide and the like.
  • antistatic agent examples include a quaternary ammonium salt type cationic surfactant, a betaine type amphoteric surfactant, an alkyl phosphate type anionic surfactant, a primary amine salt, a secondary amine salt, and a third.
  • Cationic surfactants such as tertiary amine salts, quaternary amine salts and pyridine derivatives, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, olefin sulfated ester salts, fatty alcohol sulfate ester salts, alkyl sulfates
  • Anionic surfactants such as ester salts, fatty acid ethyl sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, amber acid ester sulfonates and phosphoric acid ester salts, partial fatty acid esters of polyhydric alcohols, ethylene of fatty alcohols.
  • Nonionic surfactants such as oxide adducts, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty aminos or fatty acid amides, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, and polyethylene glycol.
  • amphoteric surfactants such as agents, carboxylic acid derivatives and imidazoline derivatives.
  • a lubricant a filler, a plasticizer, a nucleating agent, an anti-blocking agent, a foaming agent, an emulsifier, a brightener, a binder and the like may coexist.
  • the amount of the additive is usually 0.1 to 70% by mass, preferably 0.%, when the whole composition is 100% by mass. It is 1 to 50% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 15% by mass.
  • the composition for water-repellent / oil-repellent film can be prepared by appropriately mixing each component.
  • the organic silicon compound (A) and the metal compound (B) are added to a low boiling solvent (C1) to dissolve them (for example, stirring at room temperature for about 10 to 30 minutes), an aqueous solution of the catalyst (F) is added, and further.
  • Weak acid (E) is added, and a solution is prepared by, for example, stirring for about 1 to 30 hours, which is premixed with a low boiling solvent (C1), a high boiling solvent (C2) and water (D). It is preferable to dilute with a mixed solvent.
  • the dilution ratio with the mixed solvent is preferably about 5 to 1000 times by volume.
  • an additive to prepare a composition for a water-repellent / oil-repellent film.
  • composition for water-repellent / oil-repellent film of the present invention can be brought into contact with the substrate evenly by hand coating, and the hydrolyzable organic silicon compound (A) can be obtained.
  • the groups and the hydrolyzable groups of the metal compound (B) used as needed are hydrolyzed and polycondensed to form a film on the surface of the substrate.
  • the hand coating is a method in which the coating solution is impregnated into an absorber such as a cloth and applied to the base material.
  • the good hand-coating property and the evaluation of the film after hand-coating in the water-repellent / oil-repellent film composition of the present invention may be judged by actually performing hand-coating, but the hand-coating method cannot be unified.
  • the hand-coating method may be unified and the influence of hand-coating property may be judged by the superiority or inferiority of the unified method.
  • the following method is suitable as a unified method because it can reproduce a state close to actual use.
  • the moisture in the air is taken in and the hydrolyzable group is hydrolyzed. It is preferable because polycondensation is promoted.
  • the obtained film may be further dried.
  • the temperature for heating and drying is usually 40 to 250 ° C., preferably 60 to 200 ° C., and more preferably 60 to 150 ° C.
  • the base material to which the composition for water-repellent / oil-repellent film of the present invention is brought into contact is not particularly limited, and the shape of the base material 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.
  • 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, and epoxy resin. , Thermo-curable resins such as unsaturated polyesters, silicone resins, urethane resins; and the like.
  • the inorganic material include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; and alloys containing the metals.
  • the above base material may be subjected to an easy adhesion treatment in advance.
  • the easy-adhesion treatment include a hydrophilization treatment such as corona treatment, plasma treatment, and ultraviolet treatment.
  • the 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 base material in advance.
  • absorber used for the hand coating examples include cloth and sponge.
  • cloth examples include nylon, acrylic, polyester, polyurethane, polyethylene, polypropylene and the like can be used as the cloth to be used.
  • the material of the cloth is not particularly limited as long as the composition can exude, and examples thereof include woven fabrics, knitted fabrics, and non-woven fabrics.
  • the type of fiber used as the material for the woven fabric or knitted fabric is not particularly limited, and natural fiber or chemical fiber can be used.
  • natural fiber for example, plant fibers such as cotton and hemp, animal fibers such as wool, silk and cashmere can be used.
  • chemical fiber for example, nylon, acrylic, polyester, polyurethane, polyethylene, polypropylene and the like can be used.
  • the non-woven fabric include wet non-woven fabric, dry pulp non-woven fabric, dry non-woven fabric, spunbond non-woven fabric, melt blow non-woven fabric, flash spinning non-woven fabric and the like.
  • the film obtained from the composition is a silicon atom contained in the organic silicon compound (A), preferably a metal atom further contained in the metal compound (B) (preferably a silicon atom).
  • a silicon atom contained in the organic silicon compound (A), preferably a metal atom further contained in the metal compound (B) (preferably a silicon atom).
  • the structure (a1) represented by the following formula (1) is preferable as the structure in which the hydrocarbon chain-containing group (AL6 to 20) is bonded to the silicon atom.
  • R a3 represents the hydrocarbon chain-containing group (AL6 to 20)
  • Z a3 represents the hydrocarbon chain-containing group (HC) or —O— group
  • Z a3 represents the hydrocarbon chain-containing group (AL6 to 20).
  • R a3 and Z a3 may be the same or different, and among a plurality of formulas (1), R a3 and Z a3 may be the same or different. May be.
  • R a3 and Z a3 may be the same or different. May be.
  • the hydrocarbon chain-containing group (HCS) or —O— group is preferable, and —O— group is particularly preferable.
  • the structure (a1) for example, the structures represented by the following formulas (1-1) to (1-32) can be preferably exemplified.
  • the water- and oil-repellent film of the present invention is preferably a film obtained by using the metal compound (B), and the film preferably has a silicon atom to which the hydrocarbon chain-containing group (AL6 to 20) is bonded. May be bonded to a different silicon atom (second silicon atom) with the hydrocarbon chain-containing group (ALS), a hydroxy group, an alkoxy group, or a group in which a hydroxy group is condensed.
  • ALS hydrocarbon chain-containing group
  • the group in which a hydroxy group is condensed means a group —O— formed by condensing a hydroxy group with another hydroxy group, an alkoxy group, or the like, and a group in which such a hydroxy group is condensed (hereinafter, referred to as a group).
  • a condensed hydroxy group may be bonded to the second silicon atom.
  • the second silicon atom may be replaced with another metal atom (for example, Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta).
  • These second silicon atoms and other metal atoms also act as spacers due to the bonding of short hydrocarbon chain-containing groups (ALS), hydroxy groups, alkoxy groups, or condensed hydroxy groups, and the hydrocarbon chains. It is possible to enhance the water / oil repellency improving effect of the alkyl group of the containing group (AL6 to 20).
  • the alkoxy group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms.
  • a butoxy group, a propoxy group, an ethoxy group, a methoxy group and the like can be mentioned.
  • the structure (b) represented by the following formula (2) is preferable as the structure in which the hydrocarbon chain-containing group (ALS) or the hydroxy group is bonded to the second silicon atom or other metal atom.
  • R b2 represents the hydrocarbon chain-containing group (ALS) or a hydroxy group
  • a b2 represents a hydroxy group or —O—.
  • M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta.
  • n represents a number two less than the valence of M, and specifically represents an integer of 0 to 3.
  • R b2 is preferably a hydroxy group.
  • the structures represented by the following formulas (2-1) to (2-11) can be preferably exemplified.
  • the abundance ratio of the structure (a) and the structure (b) (structure (a) / structure (b)) is, for example, 0.01 or more, preferably 0.02 or more on a molar basis. , More preferably 0.03 or more, for example, 3 or less, preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less, and even more preferably 0.25 or less.
  • the thickness of the water-repellent / oil-repellent film of the present invention is usually about 1 to 50 nm. Further, even when it is formed under the scorching sun, it is excellent in water repellency and oil repellency, and both the contact angle and the sliding angle (slipperiness) are excellent. Furthermore, it has excellent hand-painting properties and has a small haze.
  • the contact angle of the water-repellent / oil-repellent film of the present invention can be evaluated by the contact angle of a water droplet having a liquid volume of 3 ⁇ L determined by the ⁇ / 2 method, and the contact angle is, for example, 97 ° or more, more preferably 100 ° or more.
  • the upper limit is not particularly limited, but is, for example, 115 °.
  • the sliding angle of water droplets having a liquid volume of 6 ⁇ L is preferably 30 ° or less, more preferably 28 ° or less, still more preferably 25 ° or less, and the lower limit. Is, for example, 5 °.
  • the haze of the water-repellent / oil-repellent film is, for example, 0.3 or less, preferably 0.15 or less, and more preferably 0.10 or less.
  • the composition for a water-repellent / oil-repellent film of the present invention has excellent storage stability. For example, even when the composition for a water-repellent / oil-repellent film after storage at a temperature of 50 ° C. for 30 days is applied by hand under the scorching sun and the contact angle, sliding angle, and haze of the obtained film are measured, the above range is measured. It is possible to be satisfied.
  • composition of the present invention since it can be hand-painted under the scorching sun, a water-repellent and oil-repellent film can be easily formed even under harsh conditions such as outdoors, which is suitable for window glass of various vehicles and buildings. Can be used.
  • the measurement method used in the examples of the present invention is as follows.
  • N-decyltrimethoxysilane 9.40 ⁇ 10 -4 mol as an organosilicon compound (A) and tetraethyl orthosilicate (tetraethoxysilane) 3.77 ⁇ 10 -3 mol as a metal compound (B) have a low boiling point. It was dissolved in 1.24 ml of isopropyl alcohol as a solvent (C1) and stirred at room temperature for 10 minutes. 1.265 ml of a 0.01 M hydrochloric acid aqueous solution as a catalyst (F) was added dropwise to the obtained solution, and the mixture was stirred for 1 hour.
  • Sample solution 1 was obtained.
  • the obtained sample solution 1 is a mixed solution of isopropyl alcohol (corresponding to a low boiling solvent (C1)), ethylene glycol as a high boiling solvent (C2), and water (corresponding to water (D)) (volume ratio is 482:
  • the coating solution 1 was prepared by diluting with a volume ratio of 150 times in 7.13: 264). The ratio (mass%) of each compound in the coating solution is as shown in Table 2 (same for other examples and comparative examples).
  • the film was prepared on a substrate heated to 50 ° C., assuming a hot sun. Specifically, after heating a glass substrate 5 ⁇ 5 cm 2 (soda lime glass, Mitsuru Kogaku Co., Ltd.) whose surface has been activated by atmospheric pressure plasma treatment to 50 ° C., 0.5 ml of a coating solution 1 is made of polyurethane. It was soaked in a non-woven fabric and applied by hand to the entire surface of the glass substrate. After the coating, a film was formed on the glass substrate by allowing it to stand at room temperature and humidity for 24 hours to cure, and the film was evaluated. Further, after storing the coating solution 1 at 50 ° C. for 30 days, a film was formed on the glass substrate in the same manner as described above, and the film was evaluated.
  • Sample solution 1 is a mixture of isopropyl alcohol (corresponding to low boiling solvent (C1)), ethylene glycol as high boiling solvent (C2), and water (corresponding to water (D)) (volume ratio 119: 1.47).
  • a coating solution and a film were prepared and evaluated in the same manner as in Example 1 except that the coating solution 2 was prepared by diluting the coating solution 2 with a volume ratio of 31.3).
  • Sample solution 1 is a mixture of isopropyl alcohol (corresponding to low boiling solvent (C1)), ethylene glycol as high boiling solvent (C2), and water (corresponding to water (D)) (volume ratio is 56.8: 0).
  • a coating solution and a film were prepared and evaluated in the same manner as in Example 1 except that the coating solution 3 was prepared by diluting with a volume ratio of .74: 15.6).
  • N-octyltriethoxysilane 9.20 ⁇ 10 -4 mol as the organosilicon compound (A) and 3.77 ⁇ 10 -3 mol of tetraethyl orthosilicate (tetraethoxysilane) as the metal compound (B) have a low boiling point. It was dissolved in 1.24 ml of isopropyl alcohol as the solvent (C1) and stirred at room temperature for 10 minutes. 1.240 ml of a 0.01 M hydrochloric acid aqueous solution as a catalyst (F) was added dropwise to the obtained solution, and the mixture was stirred for 1 hour.
  • sample solution 2 was obtained.
  • the obtained sample solution 2 is a mixed solution of isopropyl alcohol (corresponding to a low boiling solvent (C1)), ethylene glycol as a high boiling solvent (C2), and water (corresponding to water (D)) (volume ratio is 119:
  • a coating solution and a film were prepared and evaluated in the same manner as in Example 1 except that the coating solution 4 was prepared by diluting the coating solution 4 with a volume ratio of 1.47: 31.2).
  • sample solution 3 was obtained.
  • the obtained sample solution 3 is a mixed solution of isopropyl alcohol (corresponding to a low boiling solvent (C1)), ethylene glycol as a high boiling solvent (C2), and water (corresponding to water (D)) (volume ratio is 119:
  • a coating solution and a film were prepared and evaluated in the same manner as in Example 1 except that the coating solution 5 was prepared by diluting the coating solution 5 with a volume ratio of 1.47: 31.2).
  • Sample solution 1 is a mixture of isopropyl alcohol (corresponding to low boiling solvent (C1)), ethylene glycol as high boiling solvent (C2), and water (corresponding to water (D)) (volume ratio: 1376: 25.02).
  • a coating solution and a film were prepared and evaluated in the same manner as in Example 1 except that the coating solution 6 was prepared by diluting the coating solution 6 by a volume ratio of 1096).
  • Sample solution 1 is a mixture of isopropyl alcohol (corresponding to low boiling solvent (C1)), 1,3-butanediol as high boiling solvent (C2), and water (corresponding to water (D)) (volume ratio is 119).
  • the coating solution and the film were prepared and evaluated in the same manner as in Example 1 except that the coating solution 7 was prepared by diluting the coating solution 7 with a volume ratio of 1.47: 31.3).
  • the obtained sample solution 4 is a mixed solution of isopropyl alcohol (corresponding to a low boiling solvent (C1)), ethylene glycol as a high boiling solvent (C2), and water (corresponding to water (D)) (volume ratio is 119:
  • isopropyl alcohol corresponding to a low boiling solvent (C1)
  • ethylene glycol as a high boiling solvent
  • D water
  • a coating solution and a film were prepared and evaluated in the same manner as in Example 1 except that the coating solution 8 was prepared by diluting the coating solution 8 with a volume ratio of 1.47: 30.2).
  • Sample solution 1 is a mixture of isopropyl alcohol (corresponding to low boiling point solvent (C1)), propylene carbonate as high boiling point solvent (C2), and water (corresponding to water (D)) (volume ratio 120: 0.15).
  • a coating solution and a film were prepared and evaluated in the same manner as in Example 1 except that the coating solution 9 was prepared by diluting the coating solution 9 with a volume ratio of 31.3).
  • Sample solution 1 is a mixture of isopropyl alcohol (corresponding to low boiling solvent (C1)), glycerin as high boiling solvent (C2) and water (corresponding to water (D)) (volume ratio 120: 0.15: A coating solution and a film were prepared and evaluated in the same manner as in Example 1 except that the coating solution 10 was prepared by diluting the coating solution 10 times by volume in 31.3).
  • Example 1 After adding 1.000 ml of a 0.01 M hydrochloric acid aqueous solution as a catalyst (F) to the obtained solution, the mixture was stirred for 24 hours to obtain a comparative sample solution 1.
  • the obtained comparative sample solution 1 was diluted 30-fold by volume with isopropyl alcohol to prepare a comparative coating solution 1.
  • a film was prepared and evaluated in the same manner as in Example 1.
  • Example 2 After adding 1.046 ml of a 0.5 N acetic acid aqueous solution as a catalyst (F) to the obtained solution, the mixture was stirred for 24 hours to obtain a comparative coating solution 2. Other than that, a film was prepared and evaluated in the same manner as in Example 1.

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

Abstract

L'invention concerne une composition mixte contenant : un composé organique du silicium (A) dans lequel au moins un groupe hydrolysable et un groupe contenant une chaîne hydrocarbonée (AL6 à 20), qui sont des groupes alkyle en C6-C20 dans lesquels une partie d'un groupe méthylène peut être substituée par un atome d'oxygène, sont liés à un atome de silicium ; un solvant à bas point d'ébullition (C1) ayant une pression de vapeur à 20 °C supérieure à 1000 Pa et un point d'ébullition inférieur à 120 °C ; un solvant à haut point d'ébullition (C2) ayant une pression de vapeur à 20 °C d'au plus 1000 Pa et/ou un point d'ébullition d'au moins 120 °C ; et un acide faible ayant un pKa de 1 à 5.
PCT/JP2020/009079 2019-03-28 2020-03-04 Composition et film WO2020195629A1 (fr)

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WO2016068103A1 (fr) * 2014-10-31 2016-05-06 住友化学株式会社 Composition de revêtement hydrofuge/oléofuge
WO2016068118A1 (fr) * 2014-10-31 2016-05-06 住友化学株式会社 Film de revêtement transparent
JP2017201010A (ja) * 2016-04-28 2017-11-09 住友化学株式会社 皮膜
JP2017201008A (ja) * 2016-04-28 2017-11-09 住友化学株式会社 組成物
JP2018172660A (ja) * 2017-03-31 2018-11-08 住友化学株式会社 組成物
WO2019189793A1 (fr) * 2018-03-30 2019-10-03 住友化学株式会社 Composition mixte

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JP2009040936A (ja) 2007-08-10 2009-02-26 Soft99 Corporation 自動車用艶出し組成物
JP4847972B2 (ja) 2008-01-25 2011-12-28 株式会社ソフト９９コーポレーション ガラス用撥水剤
JP5566306B2 (ja) * 2009-01-13 2014-08-06 株式会社トクヤマ コーティング組成物、該組成物の製造方法、およびハードコート層を有する積層体

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JP2013213181A (ja) * 2011-09-14 2013-10-17 National Institute Of Advanced Industrial Science & Technology 有機−無機透明ハイブリッド皮膜とその製造方法
WO2016068103A1 (fr) * 2014-10-31 2016-05-06 住友化学株式会社 Composition de revêtement hydrofuge/oléofuge
WO2016068118A1 (fr) * 2014-10-31 2016-05-06 住友化学株式会社 Film de revêtement transparent
JP2017201010A (ja) * 2016-04-28 2017-11-09 住友化学株式会社 皮膜
JP2017201008A (ja) * 2016-04-28 2017-11-09 住友化学株式会社 組成物
JP2018172660A (ja) * 2017-03-31 2018-11-08 住友化学株式会社 組成物
WO2019189793A1 (fr) * 2018-03-30 2019-10-03 住友化学株式会社 Composition mixte

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