WO2017159867A1 - Film de revêtement - Google Patents

Film de revêtement Download PDF

Info

Publication number
WO2017159867A1
WO2017159867A1 PCT/JP2017/011000 JP2017011000W WO2017159867A1 WO 2017159867 A1 WO2017159867 A1 WO 2017159867A1 JP 2017011000 W JP2017011000 W JP 2017011000W WO 2017159867 A1 WO2017159867 A1 WO 2017159867A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
film
fluorine
silicon alkoxide
mass
Prior art date
Application number
PCT/JP2017/011000
Other languages
English (en)
Japanese (ja)
Inventor
怜子 日向野
和彦 山▲崎▼
大輔 ▲高▼野
常俊 本田
武志 神谷
正和 魚谷
将人 藤田
Original Assignee
三菱マテリアル電子化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱マテリアル電子化成株式会社 filed Critical 三菱マテリアル電子化成株式会社
Publication of WO2017159867A1 publication Critical patent/WO2017159867A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N13/02—Investigating surface tension of liquids
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/227—Measuring photoelectric effect, e.g. photoelectron emission microscopy [PEEM]

Definitions

  • the present invention relates to a coating.
  • This application claims priority on March 18, 2016 based on Japanese Patent Application No. 2016-055739 filed in Japan, the contents of which are incorporated herein by reference.
  • a display screen such as a liquid crystal display is desired to have various functions such as an antireflection effect and an antifouling effect. Therefore, as a material used for a display or the like, a material in which films having various functions are combined and laminated on a base material is known.
  • Patent Document 1 discloses an antifouling film-coated resin article in which an antifouling layer made of a water-repellent coating is provided on the surface of a transparent resin substrate such as an antireflection film.
  • a coating liquid prepared by mixing a silicon alkoxide, a silane compound containing a linear perfluoroalkyl group having 8 carbon atoms, and an acid over a period of about 12 hours is included.
  • An antifouling layer comprising a water-repellent coating obtained by applying a surface of an undercoat layer of a siliceous resin or an inorganic compound and drying it is disclosed.
  • silane coupling agents are also used as surface treatment agents for organic materials or inorganic materials, and it is known that various functions can be imparted to the material surface.
  • fluorine-based silane coupling agents such as fluoroalkyl group-containing silane compounds are used in various fields as imparting agents such as water repellency and oil repellency, and in particular, linear perfluoroalkyl groups having 8 or more carbon atoms. What it contains has been used.
  • PFOS perfluorooctane sulfonic acid
  • PFOA perfluorooctanoic acid
  • the present invention has been made in view of the above circumstances, and does not contain a linear perfluoroalkyl group having 8 or more carbon atoms, which is problematic in terms of bioaccumulation and environmental adaptability. It is an object to provide a film having excellent antifouling properties.
  • a film covering at least a part of the surface of the substrate When the surface of the coating is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), one or more mass spectra in the range of 83 to 952 are detected, A film containing 1.0 atomic% or more of nitrogen (N) atoms when the surface of the film is analyzed by X-ray photoelectron spectroscopy (XPS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • N nitrogen
  • a film covering at least a part of the surface of the substrate When the surface of the coating was analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), “(C m F 2m + 1 ) N ⁇ ”, “(C m F 2m + 1 ) (C n F 2n + 1 ) N -"And” (C m F 2m + 1 ) (C n F 2n + 1 ) N- (Rf 1 )-"(m and n are the same or different integers from 1 to 6; Rf 1 is from 1 to 6 carbon atoms; And any one or two or more mass spectra are detected among the linear or branched perfluoroalkylene groups), A film containing 1.0 atomic% or more of nitrogen (N) atoms when the surface of the film is analyzed by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • a film covering at least a part of the surface of the substrate When the surface of the coating was analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), “(C m F 2m + 1 ) N ⁇ ”, “(C m F 2m + 1 ) (C n F 2n + 1 ) N -"And” (C m F 2m + 1 ) (C n F 2n + 1 ) N- (Rf 1 )-"(m and n are the same or different integers from 1 to 6; Rf 1 is from 1 to 6 carbon atoms; And one or more mass spectra in the range of 83 to 952 due to any one of the linear or branched perfluoroalkylene groups) are detected, A film containing 1.0 atomic% or more of nitrogen (N) atoms when the surface of the film is analyzed by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectros
  • the film of the present invention is obtained by a film forming composition containing at least a fluorine-containing compound having a perfluoroamine structure.
  • the fluorine-containing compound having the perfluoroamine structure is not particularly limited, but specific examples include a fluorine-containing silane compound having a perfluoroamine structure represented by the following general formula (1). .
  • Rf 1 is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.
  • X is a coupling group which is a bivalent organic group.
  • R 1 is a lower alkyl group or a phenyl group, Z is a hydrolyzable group (where a is an integer of 0 to 2).
  • the coating of the present invention has high oil repellency and excellent antifouling properties without containing a linear perfluoroalkyl group having 8 or more carbon atoms, which is problematic in terms of bioaccumulation and environmental adaptability.
  • composition used to obtain the film of the present embodiment (hereinafter sometimes simply referred to as “composition”)
  • composition contains at least (A) a fluorine-containing compound having a perfluoroamine structure (hereinafter sometimes simply referred to as “fluorine-containing compound” or “component (A)”).
  • component (A) a fluorine-containing compound having a perfluoroamine structure
  • component (B) oxide fine particles having an average primary particle diameter of 2 to 50 nm
  • component (C) a hydrolyzate of silicon alkoxide (hereinafter also referred to as “component (C)”), (D) an organic solvent (hereinafter also referred to as “component (D)”), It is preferable that it is comprised including.
  • the (A) fluorine-containing compound having a perfluoroamine structure applicable to the composition described above is not particularly limited as long as it has a structure having one or more nitrogen-containing perfluoroalkyl groups in the molecule.
  • a (A) fluorine-containing compound for example, a structure having at least one nitrogen-containing perfluoroalkyl group and an alkoxysilyl group in the molecule, specifically, a perfluoroamine structure represented by the following general formula (1) Fluorine-containing silane compounds having
  • Rf 1 is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.
  • X is a linking group which is a divalent organic group.
  • X may be a linear or branched organic group.
  • X may or may not contain one or more types of bonds selected from ether bonds, ester bonds, amide bonds and urethane bonds in the molecular chain.
  • R 1 is a lower alkyl group or a phenyl group
  • Z is a hydrolyzable group (where a is an integer of 0 to 2).
  • nitrogen-containing perfluoroalkyl group in the above formula (1) include perfluoroamine structures represented by the following formulas (2) to (13).
  • examples of X in the above formula (1) include structures represented by the following formulas (14) to (17).
  • the following formula (14) is an ether bond
  • the following formula (15) is an ester bond
  • the following formula (16) is an amide bond
  • the following formula (17) is an example including a urethane bond.
  • R 2 and R 3 are hydrocarbon groups having 0 to 10 carbon atoms
  • R 4 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • R 1 is a lower alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group or a phenyl group, and among these, a methyl group is more preferable.
  • Z is not particularly limited as long as it is a hydrolyzable group that can be hydrolyzed to form a Si—O—Si bond.
  • hydrolyzable groups include alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, halogen groups such as chloro group, bromo group and iodo group, phenoxy group and naphthoxy group.
  • aryloxy groups such as benzyloxy group, aralkyloxy groups such as benzyloxy group and phenethyloxy group, acyloxy groups such as acetoxy group, propionyloxy group, butyryloxy group, valeryloxy group, pivaloyloxy group and benzoyloxy group.
  • aryloxy groups such as benzyloxy group, aralkyloxy groups such as benzyloxy group and phenethyloxy group
  • acyloxy groups such as acetoxy group, propionyloxy group, butyryloxy group, valeryloxy group, pivaloyloxy group and benzoyloxy group.
  • fluorine-containing silane compound having a perfluoroamine structure represented by the above formula (1) include structures represented by the following formulas (18) to (65).
  • R is a methyl group or an ethyl group.
  • the structure has one or more nitrogen-containing perfluoroalkyl groups in the molecule. More specifically, it has a nitrogen-containing perfluoroalkyl group in which a plurality of short-chain perfluoroalkyl groups having 6 or less carbon atoms are bonded to a nitrogen atom, and has a high fluorine content in the molecule, so that it has excellent repellency. Oiliness can be imparted.
  • the chemical structure since no perfluoroalkyl group having 8 or more carbon atoms is contained in the molecule, the chemical structure has no problem in terms of bioaccumulation and environmental adaptability.
  • the fluorine-containing compound used for the composition described above is a novel compound having excellent characteristics. That is, the fluorine-containing compound used in the above-described composition is designed to achieve both excellent oil repellency and environmental adaptability, and cannot be easily conceived from conventional compounds.
  • the fluorine-containing compound applicable to the composition for forming a film of the present embodiment is a perfluoroalkyl group having a plurality of short chain lengths branched on a nitrogen atom as a nitrogen-containing perfluoroalkyl group, that is, perfluoro Has an amine structure. Since this perfluoroamine structure is bulky, it has high oil repellency and antifouling properties compared to fluorine-containing compounds having a straight chain perfluoroalkyl structure with a short carbon number even though it has only a short chain length perfluoroalkyl group. High properties resulting from the fluorine group, such as properties, fingerprint resistance, mold release properties, moisture resistance, water resistance, and heat resistance, can be imparted.
  • the method for producing a fluorine-containing silane compound having a perfluoroamine structure represented by the above general formula (1) which is an example of a fluorine-containing compound that can be used in the above-described composition, is a nitrogen-containing compound represented by the following general formula (66). It is obtained by reducing a carboxylic acid halide having a perfluoroalkyl group to an alcohol and then reacting with an isocyanate in the presence of a metal catalyst.
  • m and n are the same or different integers of 1 to 6, respectively.
  • Rf 1 is a perfluoroalkylene group having 1 to 6 carbon atoms, and may be linear or branched.
  • Y is any one halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine.
  • the carboxylic acid halide having a nitrogen-containing perfluoroalkyl group represented by the above formula (66) can be obtained, for example, by electrolytic fluorination of a corresponding carboxylic acid ester or halide in hydrogen fluoride.
  • the carboxylic acid fluoride which has the perfluoroalkyl group obtained by the said electrolytic fluorination is hydrolyzed, and corresponding carboxylic acid is used.
  • a suitable halogenating agent eg thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, phosphorus pentabromide, hydrogen bromide, hydrogen iodide Etc.
  • a suitable halogenating agent eg thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, phosphorus pentabromide, hydrogen bromide, hydrogen iodide Etc.
  • X in the general formula (1) is a compound having an ether bond, an amide bond and a urethane bond will be described.
  • Rf 1 is a perfluoroalkylene group having 1 to 6 carbon atoms, and may be linear or branched.
  • reaction with isocyanate By reacting the alcohol represented by the above formula (67) obtained by the above reduction reaction with a trialkoxysilane, which is a silane coupling agent having an isocyanate group, in an organic solvent, the content represented by the above formula (1) is obtained. A fluorine silane compound is obtained.
  • examples of the silane coupling agent having an isocyanate group include triethoxysilylpropyl isocyanate and trimethoxysilylpropyl isocyanate.
  • a catalyst may be added to promote the reaction.
  • metal catalysts such as dibutyltin dilaurate, dibutyltin diacetate, tin octylate, bismuth octylate, bismuth decanoate, lead naphthenate, and potassium acetate, triethylamine, tripropylamine, triethylenediamine, diazabicyclone Examples thereof include amine catalysts such as decene, and trialkylphosphine catalysts.
  • the composition for forming the film of this embodiment contains (B) oxide fine particles as the component.
  • the oxide fine particles are not particularly limited as long as they are oxide fine particles (oxide nanoparticles) having an average primary particle diameter of 2 to 50 nm. Specific examples of such oxide fine particles include silica, ITO (Indium TIN Oxide), and oxides of In, Sn, Zn, Ti, or W. More specifically, indium oxide (In 2 O 3 ), tin oxide (SnO, SnO 2 , SnO 3 ), zinc oxide (ZnO), titanium oxide (TiO 2 ), tungsten oxide (WO 3 ), and the like can be given. .
  • the coating film of the present embodiment formed using this composition has high hardness and transparency of the coating film, and the film has a low refractive index so that light can be transmitted. Improves.
  • the coating film of this embodiment formed using this composition has a self-cleaning function based on a photocatalytic function and becomes a high refractive index film.
  • the antistatic function by electroconductivity can be provided to the film of this embodiment formed using this composition.
  • the average primary particle diameter of the oxide fine particles is an average of 200 particle sizes measured by image analysis among particle shapes observed with a transmission electron microscope (TEM). Value.
  • the shape of the oxide fine particles may be spherical, anisotropic flat shape, a shape connected in a bead shape, a shape in which spherical particles are connected to an indeterminate shape, or the like.
  • the average primary particle diameter of the oxide fine particles refers to a size approximated to a spherical shape by the image analysis in the above-described TEM observation.
  • the average primary particle diameter of the oxide fine particles is preferably in the range of 2 to 50 nm, more preferably in the range of 5 to 35 nm. It is preferable that the average primary particle diameter of the oxide fine particles is 2 nm or more, because oxide fine particles that exist stably can be obtained. Moreover, when the average primary particle diameter of the oxide fine particles is 50 nm or less, the transparency of the film when the composition is formed is preferably increased.
  • the average primary particle diameter of the oxide fine particles exceeds 50 nm
  • the secondary particle diameter when the aggregated particles are formed easily exceeds 200 nm. It is not preferable because it is observed.
  • oxide fine particles a mixture containing one kind or two or more kinds selected from the group listed above may be used as (B) oxide fine particles (oxide nanoparticles).
  • the composition for forming the film of this embodiment contains the hydrolyzate of (C) silicon alkoxide as the component.
  • the hydrolyzate of silicon alkoxide is not particularly limited as long as it can maintain the speed of reactivity during film formation using the film-forming composition and the hardness of the resulting film. It is not something.
  • Specific examples of the hydrolyzate of silicon alkoxide include those produced by hydrolysis (condensation) of silicon alkoxide represented by the following general formula (70). In the following formula (70), R 5 represents an alkyl group having 1 to 5 carbon atoms. Si (OR 5 ) 4 (70)
  • the hydrolyzate of (C) silicon alkoxide in the composition for forming the coating film of this embodiment, as described above, the speed of reactivity during film formation and the composition The hardness of the film of this embodiment obtained can be maintained.
  • a hydrolyzate of a silicon alkoxide having an alkyl group having 6 or more carbon atoms has a slow hydrolysis reaction, takes a long time for production, and decreases the hardness of a film obtained by applying the obtained composition. Since there is a case, it is not preferable.
  • silicon alkoxide represented by the above formula (70) examples include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, Examples include vinyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane. Of these, tetramethoxysilane and tetraethoxysilane are preferable because a film having high hardness is obtained when the coating is formed.
  • the average molecular weight of the hydrolyzate of (C) silicon alkoxide is 5 ⁇ 10 2 or more and 4 ⁇ 10 4 or less.
  • the average molecular weight is less than 5 ⁇ 10 2
  • the average molecular weight exceeds 4 ⁇ 10 4 , the composition has a high viscosity, which is not preferable because it is not suitable for coating film formation.
  • the average molecular weight of the hydrolyzate of silicon alkoxide is within the above range, it is easy to adjust the film thickness of the coating, and sufficient adhesion between the substrate and the coating can be obtained. It is preferable because it is excellent in coating properties and can be easily handled during the formation of a coating film.
  • the average molecular weight of the hydrolyzate of silicon alkoxide can be confirmed by measuring the molecular weight by GPC (Gel Permeation Chromatography). Specifically, LC10AD (manufactured by Shimadzu Corporation) is used, a guard column and LF804 (manufactured by Showa Denko KK) are used as the measurement column, the measurement temperature is 40 ° C., the mobile phase is THF, and the molecular weight is measured. Standard materials of polystyrene (PS) have molecular weights (5.0 ⁇ 10 2 , 1.99 ⁇ 10 3 , 5.97 ⁇ 10 3 , 9.11 ⁇ 10 3 , 3.79 ⁇ 10 4 , 9. The molecular weight is measured using 64 ⁇ 10 4 ).
  • GPC Gel Permeation Chromatography
  • the reason why the ratio of water is preferably within the above range is that if the ratio of water is less than the lower limit, the hydrolysis reaction may not proceed sufficiently and the hardness of the coating will decrease. On the other hand, if the upper limit value is exceeded, problems such as gelation of the reaction solution may occur during the hydrolysis reaction. In addition, the adhesion with the substrate may be reduced.
  • the ratio of water is particularly preferably 0.8 to 3.0 parts by mass.
  • water it is desirable to use ion exchange water, pure water, etc. in order to prevent mixing of impurities.
  • the inorganic acid or organic acid examples include inorganic acids such as hydrochloric acid, nitric acid, and phosphoric acid, and organic acids such as formic acid, oxalic acid, and acetic acid. Of these, it is particularly preferable to use formic acid. This is because the inorganic acid or organic acid functions as an acidic catalyst for promoting the hydrolysis reaction of silicon alkoxide, but by using formic acid as the catalyst, it is easy to form a film having excellent transparency. In addition, when formic acid is used as a catalyst, the effect of preventing the promotion of non-uniform gelation in the film after film formation is higher than when using other catalysts.
  • inorganic acids such as hydrochloric acid, nitric acid, and phosphoric acid
  • organic acids such as formic acid, oxalic acid, and acetic acid.
  • formic acid it is particularly preferable to use formic acid. This is because the inorganic acid or organic acid functions as an acidic catalyst for promoting the hydrolysis
  • the reason why the ratio of the inorganic acid or organic acid is preferably within the above range is that the ratio of the inorganic acid or organic acid is less than the lower limit value, and thus the film having high hardness is difficult to be formed. This is because even if the upper limit is exceeded, there is no effect on the reactivity, but problems such as corrosion of the coated substrate due to residual acid may occur.
  • the proportion of inorganic acid or organic acid is particularly preferably 0.008 to 0.2 parts by mass.
  • alcohol glycol ether, glycol ether acetate, or ketone
  • the reason why it is preferable to use these alcohols, glycol ethers or glycol ether acetates as the organic solvent is to improve the applicability of the composition and to facilitate mixing with, for example, silicon alkoxide.
  • Examples of the alcohol include methanol, ethanol, propanol, isopropyl alcohol (IPA), propylene glycol and the like.
  • glycol ethers ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether Etc.
  • glycol ether acetate ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether Examples include acetate and dipropylene glycol monoethyl ether acetate.
  • the ketone include methyl ethyl ketone and methyl ethyl isobutyl ketone.
  • the hydrolysis reaction is easy to control and good coating properties can be obtained during film formation, so ethanol, IPA, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or propylene glycol monomethyl Ether acetate and the like are particularly preferable.
  • the ratio of the organic solvent is preferably within the above range.
  • the reaction solution is likely to be gelled during the hydrolysis reaction, and it is difficult to obtain a film with excellent transparency. Because. In addition, the adhesion to the substrate may be reduced.
  • the upper limit is exceeded, problems such as a decrease in hydrolysis reactivity occur, and a film having sufficient hardness cannot be obtained.
  • the proportion of the organic solvent is particularly preferably 1.5 to 3.5 parts by mass.
  • the composition for forming the film of this embodiment is for adjusting the viscosity suitable for coating and for suppressing the reaction between (A) a fluorine-containing silane compound and (C) a hydrolyzate of silicon alkoxide.
  • D It is preferable to comprise an organic solvent.
  • the hydrolysis rate of silicon alkoxide is high, and a solid matter due to gelation is immediately generated.
  • the organic solvent (D) applied to the composition for forming the coating film of this embodiment is highly compatible with (C) hydrolyzate of silicon alkoxide and (A) fluorine-containing silane compound, and is used for film formation. Therefore, it is preferable to use the same organic solvents as those used when preparing the hydrolyzate of (C) silicon alkoxide described above or the organic solvents listed above.
  • ethanol IPA
  • ethylene glycol monomethyl ether ethylene glycol monomethyl ether acetate
  • propylene glycol monomethyl ether propylene glycol monomethyl ether acetate
  • propylene glycol monomethyl ether acetate and the like are particularly preferable.
  • the ratio of each solid component of the (A) fluorine-containing compound, (B) oxide fine particles, and (C) hydrolyzate of silicon alkoxide, which are the film forming components. are preferably in the required ranges with respect to the total amount of solid components (total solid components) of component (A), component (B) and component (C).
  • the contents of the components (A) to (C) in the coating film (total solid components) are each in a required range. It is preferable that
  • the lower limit of the solid component ratio of the (A) fluorine-containing compound in all the solid components may be 2% by mass or more, and may be 20% by mass or more.
  • the static contact angle of oil (n-hexadecane) is 5 ° or less.
  • the solid component ratio of the component (A) is 2% by mass or more with respect to the total amount of the solid component because water and oil repellency can be imparted to the coating film of the present embodiment.
  • the oil (n-hexadecane) has a static contact angle of 70 ° or more with respect to the coating of the present embodiment, which is preferable because the coating can be provided with oil repellency.
  • the upper limit of the solid component ratio of the component (A) may be 75% by mass or less, or 70% by mass or less.
  • the solid component ratio of the component (A) is 70% by mass or less because the film strength of the coating of the present embodiment is improved and the adhesion to the substrate is sufficient.
  • fine-particles in a solid component is 15 mass% or more with respect to the whole quantity of a solid component, and it is preferable that it is 75 mass% or less.
  • the solid component ratio of the component (B) is 20% by mass or more because oil repellency is further improved.
  • the solid component ratio of the B component is 70% by mass or less, the film strength of the coating of the present embodiment and the adhesion to the substrate are sufficiently obtained, which is preferable.
  • the solid component ratio of the hydrolyzate of (C) silicon alkoxide in the solid component is preferably 4% by mass or more, and preferably 45% by mass or less, based on the total amount of the solid component.
  • the solid component ratio of the component (C) is 10% by mass or more, the film strength of the coating of the present embodiment and the adhesion to the substrate are preferable.
  • the solid component ratio of the component (C) is 40% by mass or less, the oil repellency of the coating of this embodiment is further improved, which is preferable.
  • the particle unevenness effect of the component (B) that is, the hydrophilic film is more hydrophilic and the oil repellency film is more This is not preferable because the effect of oil repellency is reduced.
  • the solid component ratio of the hydrolyzate of (C) silicon alkoxide in the solid component is determined by the mass of the silicon alkoxide. Moreover, a temperature increase test etc. are mentioned as a method of confirming the solid content density
  • the concentration of (D) the total solid component (that is, component (A) + component (B) + component (C)) in the organic solvent is particularly limited. However, it can be appropriately selected depending on the application method to the substrate. Specifically, the concentration of all the solid components may be, for example, 1 to 50% by mass, and preferably 2 to 20% by mass.
  • a method for producing the above-described film forming composition that is, a composition containing the components (A) to (D) will be described in detail below.
  • a method for producing a composition for forming a film according to the present embodiment after producing a hydrolyzate of (C) silicon alkoxide from silicon alkoxide, (D) an organic solvent, (A) a fluorine-containing compound, and A method (first method) in which (B) oxide fine particles and the produced hydrolyzate of (C) silicon alkoxide are added and mixed may be mentioned.
  • First method Specifically, in the first method, silicon alkoxide and an organic solvent are mixed to prepare a first liquid (first step), silicon alkoxide, water, and an inorganic acid are mixed. Then, the step of preparing the second liquid (second step), the second liquid is added to the first liquid maintained at the required temperature, and the mixture is mixed while maintaining the temperature, so that the silicon alkoxide is hydrolyzed.
  • a silicon alkoxide and an organic solvent are mixed to prepare a first liquid.
  • silicon alkoxide is charged into a reaction vessel, and when the mass of the silicon alkoxide is 1, an organic solvent is added in an amount of 1.0 part by mass with respect to 1 part by mass.
  • the first liquid is prepared by stirring at a temperature of about 30 ° C. for about 15 minutes.
  • silicon alkoxide, water, and an inorganic acid are mixed to prepare a second liquid.
  • ion exchange water in an amount of 1.0 part by mass with respect to 1 part by mass of silicon alkoxide and an inorganic acid in an amount of 0.01 part by mass are put into a container and mixed.
  • the second liquid is prepared by, for example, stirring at a temperature of about 30 ° C. for about 15 minutes.
  • the second liquid is added to the first liquid maintained at a required temperature and mixed while maintaining the temperature to obtain a hydrolyzate of silicon alkoxide.
  • the first liquid prepared in the first step is maintained at a temperature of, for example, about 55 ° C. using a constant temperature liquid bath (water bath) or the like, and then the second liquid described above is added to the first liquid.
  • the liquid is added and stirred for about 60 minutes while maintaining the above temperature. Thereby, a hydrolyzate of silicon alkoxide is obtained.
  • the first method described above is a method of preparing a hydrolyzate of (C) silicon alkoxide in advance, whereas the second method has a perfluoroamine structure simultaneously with the hydrolysis of silicon alkoxide.
  • a film-forming composition is obtained by mixing a fluorine-containing compound and oxide fine particles.
  • the first ′ liquid is prepared by mixing silicon alkoxide, (A) a fluorine-containing compound and (B) oxide fine particles, and (D) an organic solvent.
  • Step (first 'step) step of mixing water and inorganic acid to prepare second' liquid (second 'step), and second' to the first 'liquid maintained at the required temperature
  • step 3 ′ step of adding the liquid and mixing while maintaining the temperature
  • a silicon alkoxide, a fluorine-containing compound having a perfluoroalkylamine structure and oxide fine particles, and an organic solvent are mixed to prepare a 1' solution.
  • silicon alkoxide is put into a reaction vessel, and when the mass of the silicon alkoxide is set to 1, an organic solvent that is 0.4 parts by mass is added.
  • the fluorine-containing compound is, for example, 0.2 to 1 part by mass
  • the oxide fine particles are, for example, 0.2 to 5 parts by mass with respect to 1 part by mass of the silicon alkoxide previously charged.
  • And are prepared, for example, by stirring for about 15 minutes at a temperature of about 30 ° C., for example.
  • the second ′ liquid is added to the first ′ liquid maintained at a required temperature and mixed while maintaining the temperature.
  • the first ′ liquid prepared in the first ′ process is maintained at a temperature of about 60 ° C. using a constant temperature bath (water bath) or the like, and then the first ′ liquid is added to the first ′ liquid. 2 'liquid is added and it stirs for about 60 minutes, maintaining the said temperature.
  • composition for forming a film described above can be applied as it is onto a workpiece such as a substrate.
  • the above-described film forming composition is applied to the surface of the base material, and then baked and cured to form a film on the surface of the base material. Can be formed.
  • the substrate is not particularly limited, but glass, plastic, metal, ceramics, stainless steel, aluminum, wood, stone, cement, concrete, fiber, fabric, paper, leather, combinations thereof, structures, laminates, and the like. Can be used.
  • the coating method on the surface of the substrate is not particularly limited. Specifically, for example, a dipping method in which the substrate is dipped in the film-forming composition, a method using an application means such as spray, spin coating, brush, roller, or a method using a printing method may be mentioned.
  • Calcination conditions can be appropriately selected depending on the type and content of the organic solvent contained in the film forming composition.
  • the firing temperature can be 60 to 200 ° C., for example.
  • the firing time can be, for example, 5 to 60 minutes.
  • the coating of this embodiment is a composition containing at least a fluorine-containing compound having a perfluoroamine structure, as shown in the general formula (1). It is formed so as to cover the part.
  • the coating of this embodiment has a perfluoroamine structure represented by the above general formula (1) when the surface of the coating is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • a mass spectrum corresponding to “(C m F 2m + 1 ) N—” derived from the fluorine-containing compound having a perfluoroamine structure represented by the general formula (1) is “ 83 CF 3 N- ”to“ 333 C 6 F 13 N— ”.
  • mass spectra corresponding to “(C m F 2m + 1 ) (C n F 2n + 1 ) N ⁇ ” include “ 152 (CF 3 ) (CF 3 ) N—” to “ 652 (C 6 F 13 ) (C 6 F 13 ) N— ”.
  • a mass spectrum corresponding to “(C m F 2m + 1 ) (C n F 2n + 1 ) N— (Rf 1 ) —” includes “ 202 (CF 3 ) (CF 3 ) N— (CF 2 ) —” to “ 952 (C 6 F 13 ) (C 6 F 13 ) N— (C 6 F 12 ) —”.
  • time of flight type secondary ion mass spectrometry (TOF-SIMS) analysis of the surface of the coating of this embodiment is performed using a time of flight type (TOF type) secondary ion mass spectrometer (for example, ULVAC-PHI). Manufactured, “PHI nano TOF II”, etc.).
  • TOF type time of flight type secondary ion mass spectrometer
  • the conditions for analysis include (primary ion source bismuth (Bi3 ++), output 30 kV, 0.3 nA, raster area 100 ⁇ 100 ⁇ m square, etc.).
  • the coating film of this embodiment is a fluorine-containing compound having a perfluoroamine structure as shown in the general formula (1) when the surface of the coating film is analyzed by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the coating of this embodiment is a fluorine-containing compound having a perfluoroamine structure as shown in the general formula (1).
  • the fluorine (F) atom derived from 3.0 atomic% or more is contained.
  • the X-ray photoelectron spectroscopy (XPS) analysis of the surface of the coating film of this embodiment can be performed using a photoelectron spectrometer (for example, “PHI5000 VersaProbe” manufactured by ULVAC-PHI).
  • the conditions for analysis include (X-ray source Monochromated AlK ⁇ ray, output 25 W, photoelectron extraction angle 45 degrees with respect to sample surface, analysis area 100 ⁇ m ⁇ , etc.).
  • a film made of a compound containing a trifluoromethyl (CF 3 ) group is known as a film showing water and oil repellency.
  • a fluoroalkylsilane (FAS) -based compound is known as a raw material for a compound containing a CF 3 group used for forming such a film.
  • FAS fluoroalkylsilane
  • C8FAS having a relatively long fluoroalkyl chains [CF 3 - (CF 2) 7 - (CH 2) 2 -Si- (OCH 3) 3]
  • C6FAS [CF 3 - (CF 2 ) 5 — (CH 2 ) 2 —Si— (OCH 3 ) 3 ] and the like have been used.
  • the film of this embodiment has a mass spectrum in the range of 83 to 952 of 1 or more when the surface of the film is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS). It is a novel film in which, when detected, when the surface of the film is analyzed by X-ray photoelectron spectroscopy (XPS), 1.0 atomic% or more of nitrogen (N) atoms are detected.
  • XPS X-ray photoelectron spectroscopy
  • the film of this embodiment is a film containing at least a fluorine-containing compound having a perfluoroamine structure as shown in the above general formula (1), which is a new raw material, instead of C6FAS and C8FAS which are conventional raw materials. Since it is obtained by the composition for formation, oil repellency is expressed on the surface of the coating.
  • the water repellency and oil repellency of the coating of this embodiment can be evaluated by contact angle measurement (droplet method).
  • the contact angle can be measured using a commercially available measuring device (for example, “Drop Master DM-700” manufactured by Kyowa Interface Science Co., Ltd.).
  • a commercially available measuring device for example, “Drop Master DM-700” manufactured by Kyowa Interface Science Co., Ltd.
  • ion-exchanged water is prepared in a syringe, and the value obtained by analyzing the contact angle after 1000 msec after water touches the surface of the coating in a stationary state by the ⁇ / 2 method is used as the water contact angle (static contact).
  • Angle, unit: ° (degree), 1 ° ( ⁇ / 180) rad).
  • n-hexadecane is prepared in a syringe, the contact angle is measured, and the value analyzed in the same manner can be used as the oil contact angle.
  • the static contact angle of water with respect to the coating film is 110 ° or more as a result of contact angle measurement. And has water repellency. Furthermore, when the composition for forming a film is prepared, a film having a super water repellency of 135 ° or more is obtained. On the other hand, the coating film of this embodiment has an oil repellency because the static contact angle of n-hexadecane with respect to the coating film is 60 ° or more.
  • preferred embodiments of the coating film of the present embodiment include a fluorine-containing compound having a perfluoroamine structure, oxide fine particles having an average primary particle diameter of 2 to 50 nm, a hydrolyzate of silicon alkoxide, an organic It is a film obtained by applying a coating liquid (composition) containing a solvent to a substrate and then baking and curing. That is, the coating film according to a preferred aspect of this embodiment includes, as solid components, a fluorine-containing compound having a perfluoroamine structure, oxide fine particles having an average primary particle diameter of 2 to 50 nm, and a hydrolyzate of silicon alkoxide. .
  • the coating film of this embodiment is a novel fluorine-containing compound having a perfluoroamine structure, which is a fluorine material with a low environmental load, oxide fine particles having an average primary particle diameter of 2 to 50 nm, and a hydrolyzate of silicon alkoxide. And an organic solvent, and a film obtained by baking and curing, a higher water repellency than a film obtained from a fluorine-containing compound having a perfluoroamine structure.
  • the film of such an embodiment has excellent antifouling properties that prevent dirt from adhering to the surface of the substrate and can be easily wiped even when adhering.
  • oxide fine particles having an average primary particle diameter of 2 to 50 nm are contained in the components of the composition for forming a film, the specific surface area is increased by the oxide fine particles in the film formed using this, Alternatively, since the particle unevenness effect is exhibited, an oil repellency film can be more oil repellant. Due to these effects, the coating film of this embodiment has higher (more excellent) oil repellency.
  • the obtained film has high scratch resistance and high hardness, and has a perfluoroamine structure. It has better adhesion to the substrate than a film obtained from the fluorine-containing compound alone.
  • the coating film of this embodiment is a cured hydrolyzate film using TEOS as the raw material silicon alkoxide and formic acid as the acidic catalyst, the transmittance is 93 to 98% and the haze is 0.4 or less. , Has excellent transparency. Therefore, even when a film is formed on a transparent substrate, excellent antifouling properties can be imparted while maintaining visibility.
  • the antifouling property of the film of this embodiment can be evaluated by, for example, the repellent property of an oil pen. Specifically, a film is formed on a substrate using the composition for forming a film, a straight line having a length of 1 cm is written on the surface of the film using an oil pen, and the ease of repelling is visually observed according to a predetermined standard. Can be evaluated.
  • the fluorine-containing silane compound having a perfluoroamine structure represented by the general formula (1) which is an example of the fluorine-containing compound having a perfluoroamine structure contained in the above-described film forming composition, has three alkoxy groups. In contrast, it has one perfluoroamine group. For this reason, it is thought that the reactivity of (A) a fluorine-containing silane compound and substrates, such as glass, is lower than the silicon alkoxide which has four general alkoxy groups. In addition, the (A) fluorine-containing silane compound has a very bulky perfluoroamine group on the opposite side in the molecule (on the opposite side) with respect to an alkoxy group highly reactive with a substrate such as glass. Therefore, it is considered that the opportunity to contact the substrate and the reaction with the substrate are further reduced.
  • a film obtained from a film-forming composition containing only the fluorine-containing silane compound having a perfluoroamine structure represented by the above general formula (1) as a solid component that is, obtained from a fluorine-containing silane compound having a perfluoroamine structure alone
  • the reactivity between the fluorine-containing silane compound and the base material is insufficient, so that it is assumed that sufficient perfluoroamine groups do not exist on the surface of the film, and high water repellency cannot be obtained.
  • the adhesiveness to the base material of the film formed becomes low.
  • the film of this embodiment is a film-forming composition containing a fluorine-containing silane compound having a perfluoroamine structure represented by the general formula (1) as a solid component and a hydrolyzate of silicon alkoxide.
  • a fluorine-containing silane compound having a perfluoroamine structure represented by the general formula (1) as a solid component
  • a hydrolyzate of silicon alkoxide When obtained, it is considered that the hydrolyzate of silicon alkoxide contained as a solid component functions so as to increase the reactivity with the substrate and the like.
  • the film of the present embodiment is obtained from a film-forming composition containing oxide fine particles having an average primary particle diameter of 2 to 50 nm, it is contained as a solid component in the film-forming composition. It is considered to function so as to exhibit higher water repellency due to the particle unevenness effect of the oxide fine particles.
  • the inventors of the present application have (A) only a fluorine-containing compound, and (B) oxide fine particles and (C) silicon alkoxide hydrolyzate.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • detection of a mass spectrum in the range of 83 to 952 is not clear, and the surface of the coating is analyzed by X-ray photoelectron spectroscopy.
  • XPS X-ray photoelectron spectroscopy
  • the detected value by XPS measurement is that the nitrogen (N) atom is 1.0 atom or more and the fluorine (F) atom is 3.0 atom% or more, and (B) oxide fine particles and ( C) It has been found that there is a correlation with the inclusion of a hydrolyzate of silicon alkoxide.
  • the presence of (C) a hydrolyzate of silicon alkoxide in the coating creates a coating with higher adhesion to the substrate, and at the same time, (A) the fluorine-containing compound is aligned on the surface of the coating. It becomes possible to make it easier. For this reason, the coating film exhibits a high antifouling function, and at the same time, when XPS measurement is performed on the surface of the coating film, high detection values of N and F are obtained.
  • a mass spectrum in the range of 83 to 952 is detected, and the coating contains (B) oxide fine particles and (C) hydrolyzate of silicon alkoxide. And found that there is a correlation. Specifically, when (B) oxide fine particles and (C) silicon alkoxide hydrolyzate are present in the coating, a large number of (A) fluorine-containing compounds can be present on the outermost surface of the coating. Therefore, a mass spectrum in the range of 83 to 952 can be clearly detected when analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS) suitable for analysis of the pole surface.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the inventors of the present application analyzed a surface of a substrate covering at least a part of the surface of the substrate by analyzing the surface of the coating by time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • XPS X-ray photoelectron spectroscopy
  • N nitrogen atoms are contained by 1.0 atomic% or more
  • the structure of the coating film includes (A) a fluorine-containing compound, (B) oxide fine particles, and (C) a hydrolyzate of silicon alkoxide.
  • the surface is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), a mass spectrum in the range of 83 to 952 is clearly detected, and the surface is analyzed by X-ray photoelectron spectroscopy ( When analyzed by XPS), a film in which nitrogen (N) atoms are detected at 1.0 atom or more and fluorine (F) atoms is detected at 3.0 atom% or more is (A) a fluorine-containing compound, (B) oxidation It is possible to specify that the structure includes physical particles and a hydrolyzate of (C) silicon alkoxide.
  • the coating film of the present embodiment high oil repellency and excellent properties are obtained without containing a linear perfluoroalkyl group having 8 or more carbon atoms, which is a problem in terms of bioaccumulation and environmental adaptability. It is possible to provide a film having antifouling properties.
  • the coating film of this embodiment is composed of a composition containing a plurality of short-chain-length perfluoroalkyl groups branched on a nitrogen atom as the nitrogen-containing perfluoroalkyl group, that is, a fluorine-containing compound having a perfluoroamine structure.
  • a fluorine-containing compound having a perfluoroamine structure can get. Since this perfluoroamine structure is bulky, it has higher oil repellency than a fluorine-containing compound having a linear perfluoroalkyl structure having 8 or more carbon atoms, even though it has only a perfluoroalkyl group with a short chain length structure. It is possible to obtain high characteristics due to the above-described fluorine group.
  • the coating film of this embodiment contains oxide fine particles having an average primary particle diameter of 2 to 50 nm, a very high water repellency is obtained due to a synergistic effect including the fluorine-containing compound having a perfluoroamine structure and the oxide fine particles. And excellent antifouling properties. It also has excellent transparency and adhesion to the substrate.
  • the coating of this embodiment when the surface is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), a mass spectrum in the range of 83 to 952 is clearly detected, and
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • XPS X-ray photoelectron spectroscopy
  • N nitrogen
  • F fluorine
  • the composition includes a hydrofluoric compound of (B) oxide compound, (B) oxide fine particles, and (C) silicon alkoxide.
  • the technical scope of the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.
  • the coating film may contain two or more fluorine-containing compounds, or may contain a hydrolyzate of two or more silicon alkoxides.
  • the mixture was stirred at room temperature for 1 hour, and then the reaction solution was quenched with water and an aqueous hydrochloric acid solution, and chloroform was added for liquid separation.
  • the obtained chloroform layer was washed with an aqueous hydrochloric acid solution and water and dried over magnesium sulfate, and then the obtained solution was concentrated by a rotary evaporator. Furthermore, the obtained solution was distilled under reduced pressure to obtain an alcohol form (171.0 g, yield 68%).
  • the mixture was stirred at room temperature for 1 hour, washed with an aqueous sodium hydroxide solution and water, dried by adding magnesium sulfate. After magnesium sulfate was filtered off, the resulting solution was concentrated by a rotary evaporator. Furthermore, the allylamide body (21.0 g, yield 60%) was obtained by distilling the obtained solution under reduced pressure.
  • oxide fine particle dispersion As an example of oxide fine particles, the following (1) to (7) were used as oxide fine particles or a dispersion of oxide fine particles.
  • Titania particles having an average primary particle size of 10 nm are solid
  • ATO particles with an average primary particle size of about 20 nm are propylene glycol monomethyl ether Dispersed in solvent
  • a hydrolyzate of silicon alkoxide was prepared by the following method. Specifically, first, tetraethoxysilane (TEOS) was prepared as a silicon alkoxide and charged into a separable flask. When the mass of the silicon alkoxide is 1, the amount of ethanol to be 1.0 part by mass is added as an organic solvent with respect to 1 part by mass, and the mixture is stirred at a temperature of 30 ° C. for 15 minutes. A liquid was prepared.
  • TEOS tetraethoxysilane
  • 1.0 part by mass of ion-exchanged water with respect to 1 part by mass of silicon alkoxide and 0.01 parts by mass of nitric acid are used as inorganic acids in the beaker.
  • the second liquid was prepared by charging and mixing and stirring at a temperature of 30 ° C. for 15 minutes.
  • the prepared first liquid was maintained at a temperature of 55 ° C. in a water bath, the second liquid was added to the first liquid, and the mixture was stirred for 60 minutes while maintaining the temperature.
  • a hydrolyzate (C) average molecular weight: 4 ⁇ 10 3 ) of silicon alkoxide having a solid content of 10% by mass in terms of SiO 2 was obtained.
  • hydrolysates (C) of silicon alkoxides having different average molecular weights (average molecular weights: 1 ⁇ 10 3 , 2 ⁇ 10 4 ) having a solid content of 10% by mass in terms of SiO 2 were prepared.
  • Example 1 As an organic solvent, 47.0 g of ethanol is prepared, and 0.7 g of a compound represented by the formula (72) described in the above synthesis example is added as a fluorine-containing compound (A) having a perfluoroamine structure. Thereafter, 1.3B of an IPA dispersion containing silica particles having an average primary particle size of 12 nm as oxide fine particles (B) at a solid content of 15% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 1.0 g of (average molecular weight: 4 ⁇ 10 3 ) was added to prepare a film forming composition. Table 1 shows the component composition.
  • a slide glass is used as an object to be processed (base material), the film-forming composition is applied by a spin coating method, and the obtained film is baked at 120 ° C. for 30 minutes to obtain an evaluation member (film). It was.
  • Example 2 41.3 g of IPA is prepared as an organic solvent, and 0.5 g of a compound represented by the general formula (71) described in the above synthesis example is weighed and added as a fluorine-containing compound (A) having a perfluoroamine structure. Thereafter, (B) 3.3 g of a propylene glycol monomethyl ether dispersion in which silica particles having an average primary particle size of 10 nm as oxide fine particles are contained at a solid content of 15% by mass, and the above-prepared (C) silicon alkoxide prepared in advance 4.9 g of hydrolyzate (average molecular weight: 4 ⁇ 10 3 ) was added to prepare a film-forming composition. Table 1 shows the component composition. Further, an evaluation member (film) was obtained in the same manner as in Example 1 described above.
  • Example 3 As an organic solvent, 42.2 g of propylene glycol monomethyl ether is prepared, and 0.3 g of a compound represented by the above formula (73) is weighed and added as a fluorine-containing compound (A) having a perfluoroamine structure. Thereafter, (B) 1.5 g of an ethanol dispersion containing zirconia particles having an average primary particle diameter of 20 nm as an oxide fine particle at a solid content of 40% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 6.0 g of (average molecular weight: 4 ⁇ 10 3 ) was added to prepare a film forming composition. Table 1 shows the component composition. Further, an evaluation member (film) was obtained in the same manner as in Example 1 described above.
  • Example 4 As an organic solvent, 43.5 g of ethanol is prepared, and 0.5 g of a compound represented by the general formula (74) described in the above synthesis example is weighed and added as a fluorine-containing compound (A) having a perfluoroamine structure. Thereafter, (B) 2.4 g of an IPA dispersion containing silica particles having an average primary particle size of 12 nm as oxide fine particles at a solid content of 15% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 3.6 g of (average molecular weight: 4 ⁇ 10 3 ) was added to prepare a film forming composition. Table 1 shows the component composition. Further, an evaluation member (film) was obtained in the same manner as in Example 1 described above.
  • Example 5 As an organic solvent, 42.2 g of propylene glycol monomethyl ether is prepared, and 0.3 g of a compound represented by the above formula (75) described in the above synthesis example is weighed and added as a fluorine-containing compound (A) having a perfluoroamine structure. . Thereafter, (B) 1.5 g of an ethanol dispersion containing zirconia particles having an average primary particle diameter of 20 nm as an oxide fine particle at a solid content of 40% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 6.0 g of (average molecular weight: 4 ⁇ 10 3 ) was added to prepare a film forming composition. Table 1 shows the component composition. Further, an evaluation member (film) was obtained in the same manner as in Example 1 described above.
  • Example 6 As an organic solvent, 41.8 g of ethanol is prepared, and 0.2 g of a compound represented by the formula (71) described in the above synthesis example is added as a fluorine-containing compound (A) having a perfluoroamine structure. Then, (B) hydrolyzate of the above-mentioned (C) silicon alkoxide prepared in advance with 5.6 g of an ethanol dispersion containing titania particles having an average primary particle diameter of 10 nm as oxide fine particles at a solid content of 10% by mass 2.4 g of (average molecular weight: 4 ⁇ 10 3 ) was added to prepare a film forming composition. Table 1 shows the component composition. Further, an evaluation member (film) was obtained in the same manner as in Example 1 described above.
  • Example 7 As an organic solvent, 46.3 g of propylene glycol monomethyl ether is prepared, and 1.1 g of a compound represented by the general formula (72) described in the above synthesis example is weighed and added as a fluorine-containing compound (A) having a perfluoroamine structure. . Thereafter, (B) 1.8 g of a propylene glycol monomethyl ether dispersion in which ATO particles having an average primary particle size of 20 nm as an oxide fine particle are contained at a solid content of 20% by mass, and the above-prepared (C) silicon alkoxide prepared in advance 0.8 g of hydrolyzate (average molecular weight: 2 ⁇ 10 4 ) was added to prepare a film forming composition. Table 1 shows the component composition. Further, an evaluation member (film) was obtained in the same manner as in Example 1 described above.
  • tetraethoxysilane (TEOS) is prepared as a silicon alkoxide and charged into a separable flask.
  • the compound represented by the general formula (73) is 0.5 parts by mass as the fluorine-containing compound (A) having a perfluoroamine structure with respect to 1 part by mass.
  • 1.1 parts by mass of ethanol was added as an organic solvent, and the mixture was stirred at a temperature of 30 ° C. for 15 minutes to prepare a first liquid.
  • an amount of oxide fine particles (silica particles having an average primary particle diameter of about 15 nm) in an amount of 1 part by mass was added. Table 1 shows the component composition.
  • ion exchange water in an amount of 0.85 parts by mass and nitric acid in an amount of 0.01 parts by mass with respect to 1 part by mass of silicon alkoxide are charged into the beaker as inorganic acids.
  • a second liquid was prepared by stirring at a temperature of 30 ° C. for 15 minutes.
  • the second liquid was added to the first liquid and stirred for 60 minutes while maintaining the temperature.
  • the hydrolyzate (C) of silicon alkoxide containing the fluorine-containing compound (A) having a perfluoroamine structure represented by the above formula (73) was obtained.
  • tetraethoxysilane is prepared as a silicon alkoxide and charged into a separable flask.
  • the compound represented by the general formula (74) is 0.5 parts by mass as the fluorine-containing compound (A) having a perfluoroamine structure with respect to 1 part by mass.
  • 1.1 parts by mass of ethanol was added as an organic solvent, and the mixture was stirred at a temperature of 30 ° C. for 15 minutes to prepare a first liquid.
  • an amount of oxide fine particles sica particles having an average primary particle diameter of about 15 nm
  • Table 1 shows the component composition.
  • ion exchange water in an amount of 0.85 parts by mass and nitric acid in an amount of 0.01 parts by mass with respect to 1 part by mass of silicon alkoxide are charged into the beaker as inorganic acids.
  • a second liquid was prepared by stirring at a temperature of 30 ° C. for 15 minutes.
  • the second liquid was added to the first liquid and stirred for 60 minutes while maintaining the temperature.
  • a hydrolyzate (C) of silicon alkoxide containing a fluorine-containing compound (A) having a perfluoroamine structure represented by the above formula (74) was obtained.
  • Example 10 As an organic solvent, 46.4 g of IPA is prepared, and 0.6 g of a compound represented by the general formula (71) described in the above synthesis example is weighed and added as a fluorine-containing compound (A) having a perfluoroamine structure. Thereafter, (B) 1.0 g of an ethanol dispersion in which ITO particles having an average primary particle size of 30 nm as oxide fine particles are contained at a solid content of 20% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 2.0 g of (average molecular weight: 1 ⁇ 10 3 ) was added to prepare a film forming composition. Table 1 shows the component composition. Further, an evaluation member (film) was obtained in the same manner as in Example 1 described above.
  • Example 11 42.2 g of IPA is prepared as an organic solvent, and 0.5 g of a compound represented by the general formula (75) described in the above synthesis example is weighed and added as a fluorine-containing compound (A) having a perfluoroamine structure. Thereafter, (B) 2.4 g of an ethanol dispersion in which ITO particles having an average primary particle diameter of 30 nm as oxide fine particles are contained at a solid content of 20% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 4.9 g of (average molecular weight: 1 ⁇ 10 3 ) was added to prepare a film forming composition. Table 1 shows the component composition. Further, an evaluation member (film) was obtained in the same manner as in Example 1 described above.
  • the evaluation members (coating films) obtained in Examples 1 to 11 and Comparative Examples 1 to 4 were measured by X-ray photoelectron spectroscopy (XPS) on the surface of the film to qualitatively and quantitatively analyze the surface detection elements. Went.
  • the X-ray photoelectron spectroscopic analysis was performed using ULPHI Phi, PHI5000 VersaProbe, the X-ray source was Monochromated AlK ⁇ ray, the output was 25 W, the photoelectron extraction angle was 45 degrees with respect to the sample surface, and the analysis area was 100 ⁇ m ⁇ .
  • the qualitative analysis by the survey spectrum, the Narrow spectrum measurement and quantitative calculation of the detected element were performed, and the atomic% ratio of each element was obtained.
  • the evaluation results are shown in Table 2.
  • Comparative Example 1 since the material resulting from F and N (that is, the material corresponding to the fluorine-containing compound (A)) was not included, both F and N were not detected in the XPS measurement. Further, as a result of measurement using TOF-SIMS as a peak due to other materials such as SiO 2 , Mw137 was the maximum peak.
  • Comparative Example 3 an amine-based silane coupling agent containing “C6FAS” and N was used in place of the fluorine-containing compound (A). Therefore, in the measurement using TOF-SIMS, the amine-based coupling agent “C Mw58 due to the structure of “ 3 H 6 NH 2 ” was detected. However, in Comparative Example 4, it was confirmed that the oil repellency of the surface of the coating film was greatly reduced due to the addition of the amine-based silane coupling agent, and the antifouling property was low.
  • the coating contains only the fluorine-containing compound (A), but the coating does not contain (B) oxide fine particles and (C) a hydrolyzate of silicon alkoxide.
  • a peak was detected at Mw69, but a peak at Mw452 due to the structure of “(C 4 F 9 ) 2 —N” was not detected.
  • the detected amount of N was less than 1 atomic%, and the detected amount of F was less than 3.0 atomic%.
  • the coating of the present invention is a coating agent that imparts various properties such as antifouling properties, fingerprint resistance, water and oil repellency, mold release properties, moisture resistance, water resistance, lubricity, and heat resistance, and a paint that imparts heat resistance. It is useful in a wide range of applications such as surface treatment agents such as additives.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Materials Engineering (AREA)
  • Paints Or Removers (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)

Abstract

Le film de revêtement de l'invention revêt au moins une partie de la surface d'un matériau de base. Lorsque la surface de ce film de revêtement est analysée par une spectrométrie de masse des ions secondaires à temps de vol (TOF-SIMS), un spectre de masse ou plus compris dans une plage de 83 à 952 est détecté, et simultanément lorsque la surface de ce film de revêtement est analysée par une spectroscopie de photoélectrons X (XPS), un atome d'azote (N) est contenu à raison de 1,0% atomique ou plus.
PCT/JP2017/011000 2016-03-18 2017-03-17 Film de revêtement WO2017159867A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016055739A JP2017170629A (ja) 2016-03-18 2016-03-18 被膜
JP2016-055739 2016-03-18

Publications (1)

Publication Number Publication Date
WO2017159867A1 true WO2017159867A1 (fr) 2017-09-21

Family

ID=59851683

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/011000 WO2017159867A1 (fr) 2016-03-18 2017-03-17 Film de revêtement

Country Status (2)

Country Link
JP (1) JP2017170629A (fr)
WO (1) WO2017159867A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019077744A (ja) * 2017-10-20 2019-05-23 三菱マテリアル電子化成株式会社 ウエットシート用液組成物及びウエットシート

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6986408B2 (ja) * 2017-09-29 2021-12-22 三菱マテリアル電子化成株式会社 膜形成用液組成物の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1129585A (ja) * 1997-07-04 1999-02-02 Shin Etsu Chem Co Ltd パーフルオロポリエーテル変性アミノシラン及び表面処理剤
JPH11217561A (ja) * 1998-02-03 1999-08-10 Shin Etsu Chem Co Ltd 撥水膜復活剤
CN1315483A (zh) * 2000-03-29 2001-10-03 中国科学院化学研究所 一种超双疏（疏水、疏油）表面处理剂和用途
JP2011505422A (ja) * 2007-12-04 2011-02-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フルオロアルキルシラン
JP2015196644A (ja) * 2014-03-31 2015-11-09 三菱マテリアル株式会社 含フッ素シラン化合物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1129585A (ja) * 1997-07-04 1999-02-02 Shin Etsu Chem Co Ltd パーフルオロポリエーテル変性アミノシラン及び表面処理剤
JPH11217561A (ja) * 1998-02-03 1999-08-10 Shin Etsu Chem Co Ltd 撥水膜復活剤
CN1315483A (zh) * 2000-03-29 2001-10-03 中国科学院化学研究所 一种超双疏（疏水、疏油）表面处理剂和用途
JP2011505422A (ja) * 2007-12-04 2011-02-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フルオロアルキルシラン
JP2015196644A (ja) * 2014-03-31 2015-11-09 三菱マテリアル株式会社 含フッ素シラン化合物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019077744A (ja) * 2017-10-20 2019-05-23 三菱マテリアル電子化成株式会社 ウエットシート用液組成物及びウエットシート

Also Published As

Publication number Publication date
JP2017170629A (ja) 2017-09-28

Similar Documents

Publication Publication Date Title
KR102120626B1 (ko) 반사 방지층이 형성된 기재
JP5768805B2 (ja) パーフルオロポリエーテル変性ポリシラザン及びその製造方法、表面処理剤並びに該表面処理剤で処理された物品
TWI691505B (zh) 膜形成用液體組成物及其製造方法
JP6154829B2 (ja) 疎油性コーティング
US9611399B2 (en) Fluorinated coatings with lubricious additive
JP2009144133A (ja) パーフルオロポリエーテル変性シラン化合物、これを含有する防汚性コーティング剤組成物およびこれを適用した膜
JPWO2017212850A1 (ja) フルオロポリエーテル基含有ポリマー、表面処理剤及び物品
WO2017159854A1 (fr) Composition formant un revêtement, son procédé de production et revêtement
WO2000034408A1 (fr) Article optique, procede de fabrication associe et compose organo-silicie
JPWO2017022638A1 (ja) モバイルディスプレイ機器のカバーガラス等に好適なガラス基板
JP6319905B2 (ja) 被膜形成用組成物及びその製造方法、並びに被膜
JP2015034281A (ja) 紫外線遮蔽被膜付き板ガラスとその製造方法、及び紫外線遮蔽被膜付き板ガラスの被膜形成用塗布液
TW201739787A (zh) 含有氟聚醚基之聚合物改質矽烷、表面處理劑及物品
JP2017132926A (ja) 被膜形成用組成物及びその製造方法、並びに被膜
WO2012081524A1 (fr) Composé fluoré, composition de revêtement, matériau de base comportant une couche hydrophobe, et son procédé de production
WO2017159867A1 (fr) Film de revêtement
JP5731037B1 (ja) 含フッ素シラン化合物
JP2019183110A (ja) 撥水性被膜形成用組成物及び撥水性被膜
JP6694718B2 (ja) 親水撥油性回復剤及び親水撥油性被膜の親水撥油性の回復方法、並びに親水撥油性被膜
JP2018172646A (ja) 組成物
JP2022017640A (ja) 撥水撥油性膜形成用液組成物及びその製造方法
JP7231422B2 (ja) 防汚性膜
JPWO2020137992A1 (ja) 撥水撥油層付き基材、蒸着材料および撥水撥油層付き基材の製造方法
JP2016050276A (ja) 塗装鋼板用表面処理剤
JP7177889B2 (ja) 膜形成用液組成物

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17766862

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17766862

Country of ref document: EP

Kind code of ref document: A1