WO2020175121A1 - Surface treatment agent, production method therefor, and surface treatment method - Google Patents

Surface treatment agent, production method therefor, and surface treatment method Download PDF

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Publication number
WO2020175121A1
WO2020175121A1 PCT/JP2020/005064 JP2020005064W WO2020175121A1 WO 2020175121 A1 WO2020175121 A1 WO 2020175121A1 JP 2020005064 W JP2020005064 W JP 2020005064W WO 2020175121 A1 WO2020175121 A1 WO 2020175121A1
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Prior art keywords
surface treatment
treatment agent
group
copolymer
formula
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PCT/JP2020/005064
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French (fr)
Japanese (ja)
Inventor
雄太 青海
英夫 澤田
健一 土澤
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藤倉コンポジット株式会社
国立大学法人弘前大学
日東紡績株式会社
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Publication of WO2020175121A1 publication Critical patent/WO2020175121A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a surface treatment agent and a method for producing the same, and a surface treatment method using the surface treatment agent.
  • the static separation technique has a problem that it takes a lot of time
  • the centrifugal separation technique has a problem that a large-scale device is required
  • the adsorption separation technique has a large amount of oil-containing wastewater.
  • a problem that it is not suitable for processing Conventionly, a composite material in which a predetermined fluorine compound and an inorganic compound are nanocomposited, and an oil/water separation membrane in which fluorine-containing nanocomposite particles having hydrophilicity/oil repellency are carried on filter paper or nonwoven fabric is used. Proposed (see Patent Document 1)
  • a method for preventing oil stains attached to the surface of an article a method is known in which the article surface is treated with a surface-treating agent having oil repellency to form an antifouling film on the article surface.
  • a surface treatment agent having oil repellency fluororesins such as polytetrafluoroethylene (Temono) and polychlorotrifluoroethylene are widely used.
  • fluororesins have high water repellency, it is difficult to wash away oil stains attached to the surface of articles by washing with water. Therefore, it is desired to propose a surface treatment agent having oil repellency for preventing oil stains and hydrophilicity for washing adhered oil stains with water.
  • a copolymer containing a perfluoroalkyl (meth)acrylic acid ester having 1 to 18 carbon atoms and a hydrophilic group-containing monomer as constituent components is known (see Patent Document 2).
  • Patent Document 1 Japanese Patent Laid-Open No. 20 1 5 _ 1 8 7 2 20
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2 0 0 8 — 2 9 7 4 8 2
  • the present invention provides a surface treatment agent capable of imparting excellent hydrophilicity and oil repellency, a method for producing the same, a surface treatment base material capable of exhibiting excellent hydrophilicity and oil repellency, and an object to be treated. It is an object of the present invention to provide a surface treatment method capable of imparting excellent hydrophilicity and oil repellency to the surface of a treated substrate.
  • the present invention provides a fluorine-containing compound represented by the following formula (1), a quaternary ammonium salt of allylamine and a copolymer of an amide compound or carboxylic acid, and a solvent.
  • a surface treatment agent comprising:
  • the copolymer may have a chemical structure represented by the following formula (2), or may have a chemical structure represented by the following formula (3):
  • the content ratio (mass basis) of the fluorine-containing compound and the copolymer is 1:1 to
  • the solvent may be an alcohol solvent having 1 to 5 carbon atoms.
  • 'and rod 2' represents an alkyl group having 1-4 carbon atoms each independently, X- represents a halide ion, an inorganic anion or an organic anion.
  • the present invention comprises a base having a first surface and a second surface facing the first surface, and a surface treatment layer provided on at least the first surface of the base, wherein the surface treatment is performed.
  • the layer provides a surface-treated base material, which is formed by subjecting the first surface of the base to a surface treatment using the surface-treating agent.
  • the present invention is characterized by mixing a fluorine-containing compound represented by the following formula (1), a copolymer of quaternary ammonium salt of allylamine and an amide compound or carboxylic acid, and a solvent:
  • a method for producing a treating agent is provided. In such a production method, it is preferable that neither an acid catalyst nor an alkali catalyst is mixed.
  • the present invention provides a surface treatment method characterized by subjecting a substrate to be treated to a surface treatment using the above-mentioned surface treatment agent.
  • a surface treatment agent capable of imparting excellent hydrophilicity and oil repellency a method for producing the same, a surface treated substrate capable of exhibiting excellent hydrophilicity and oil repellency, and a treated substrate
  • a surface treatment method that can impart excellent hydrophilicity and oil repellency to the surface of ⁇ 2020/175 121 5 boxes (: 171-1? 2020 /005064
  • the surface treatment agent according to the present embodiment contains a fluorine-containing compound represented by the following formula (1), a quaternary ammonium salt of allylamine and a copolymer of an amide compound or a carboxylic acid, and a solvent.
  • a surface treatment agent contains a reaction product of the above-mentioned fluorine-containing compound and the above-mentioned copolymer in a micelle state, and can be prepared as a reaction solution when producing the micelle-like reaction product. ..
  • formula (1) represents a group containing a fluoroalkyl group, represents an alkyl group or an alkoxyalkyl group, Each independently represent a hydrogen atom or a monovalent organic group, X is an integer of 1 to 100, and V is an integer of 0 to 100.
  • the alkyl group represented by, for example, a methyl group, an alkyl group having 1 to 2 carbon atoms such as an ethyl group, Arco represented by ⁇ 02020/175 121 6 (: 17 2020/005064
  • Examples of the xyalkyl group include alkoxyalkyl groups having 2 to 4 carbon atoms such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group and an ethoxyethyl group.
  • the group represented by is preferably an alkyl group, and particularly preferably a methyl group.
  • the number of the intermediate chain (one CH 2 -CH -) to which the trialkoxysilyl group or trialkoxyalkoxysilyl group (1 3 I ( ⁇ [3 ⁇ 4 2 ) 3 ) is bonded is It is 1 to 100, preferably 1 to 50, more preferably 1 to 10 and particularly preferably 2 to 5.
  • the middle chain (10 The number of s is 0 to 100, preferably 0 to 50, and more preferably 0 to 10.
  • Examples of compounds suitable as the fluorine-containing compound include compounds represented by the following formulas (5) to (9).
  • the proportion of fluorine atoms occupied in one molecule is large.
  • the reaction for producing the nanocomposite particles according to the present embodiment can be efficiently advanced.
  • X′ is 2 or 3.
  • Equation (6) and the formula (7) is ten ( ⁇ 3) hundred 2 ⁇ ( ⁇ 3) a group represented by the hundred 3 7.
  • X 3 is an integer of 1 to 100.
  • X-shallow is an integer of 1 to 100 and Suk-oh is an integer of 1 to 500.
  • X ⁇ is an integer from 1 to 10 and so ⁇ is an integer from ⁇ to 100.
  • X is an integer of 1 to 10 and V is an integer of 0 to 100.
  • the fluorine-containing compound represented by the above formula (1) is obtained by reacting a monomer represented by the following formula () with a monomer represented by the following formula in the presence of a fluorine-containing peroxide represented by the following formula (3). It is obtained by polymerizing with a single body of the formula (I 0 ).
  • the reaction product (fluorine-containing compound) may contain an oligomer in which the group () containing a fluoroalkyl group is introduced only at one end, at an arbitrary ratio.
  • formulas (I 3) to (I 0 ) represents a group containing a fluoroalkyl group, represents an alkyl group or an alkoxyalkyl group, and represents each independently a hydrogen atom or a monovalent organic group.
  • the surface treatment agent according to the present embodiment contains a copolymer of a quaternary ammonium salt of allylamine and an amide compound, or a copolymer of a quaternary ammonium salt of allylamine and carboxylic acid.
  • a copolymer of a quaternary ammonium salt of allylamine and an amide compound or a copolymer of a quaternary ammonium salt of allylamine and carboxylic acid.
  • the quaternary ammonium salt of allylamine which is a constituent of these copolymers, include diallyldialkylammonium chloride, diallyldialkylammonium alkylsulfate, diallyldialkylammonium hydroxide, diallyldialkylammonium fluoride and the like.
  • diallyldialkylammonium chlorides include diallyldimethylammonium chloride, diallylethylmethylammonium chloride, diallylethylylammonium chloride and the like. ⁇ 2020/175 121 9 (:171? 2020/005064
  • diallylalkylammonium alkylsulfates include diallyldimethylammonium methylsulfate, diallylmethylammonium methylsulfate, diallylditylammonium methylsulfate, diallyldimethylammoniumethylsulfate, diallylethyl.
  • diallylalkylammonium alkylsulfates include diallyldimethylammonium methylsulfate, diallylmethylammonium methylsulfate, diallylditylammonium methylsulfate, diallyldimethylammoniumethylsulfate, diallylethyl.
  • Examples include methylammonium ethyl sulfate and diallyl tylethyl ammonium ethyl sulfate.
  • diallyldialkylammonium hydroxide examples include diallyldimethylammonium hydroxide, diallylethylmethylammonium hydroxide, diallyldiethylammonium hydroxide and the like.
  • diallyldialkylammonium fluoride examples include diallyldimethylammonium fluoride, diallylethylammonium fluoride, diallyljetylammonium fluoride and the like.
  • Examples of the amide compound that is a constituent component of the above-mentioned copolymer include acrylic amide, alkyl acrylate, dialkyl acrylate, aminoalkyl acrylate, hydroxyalkyl acrylate, and the like.
  • Examples of the carboxylic acid include monocarboxylic acids such as acrylic acid and methacrylic acid; dicarboxylic acids such as maleic acid and fumaric acid.
  • Examples of the above-mentioned copolymer include those having a chemical structure represented by the following formula (2) or the following formula (3), and the like: 8 3 -" 1 4 1, 8 3 -" 1 8 1,?
  • Commercially available products such as 8 3 -" 1 8 1 1_, 8 3 -2 3 5 1, 8 3 -2 4 5 1 (all product names, manufactured by Nittobo Medical Co., Ltd.) may be used.
  • X- represents a halide ion, an inorganic anion or an organic anion.
  • alkyl group represented by [4′] examples include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group.
  • examples of the halide ion represented by X- include a fluoride ion (_), a chloride ion ( ⁇ ), and the like.
  • hydroxide ion ( ⁇ 1 to 1 _), hydrogen sulfate ion (1 to 13 ⁇ 4 _), nitrate ion (1 ⁇ 10 ⁇ 3- ), and the like
  • organic anion includes, for example, methyl. sulfate ion (Rei_1 ⁇ 1 3 3_Rei 4) alkyl sulfate ion such as acetate ion ( ⁇ 1-1 3 ⁇ _ ⁇ _ ⁇ -) and the like.
  • Examples of the copolymer having the chemical structure represented by the formula (2) include, for example, diallyldimethylammonium chloride ⁇ acrylic amide copolymer represented by the following formula (2-1) (for example, Nitovo 8-3_" 41 1, 8 3-" 81, ?8 3-" 81 1_, etc. manufactured by Medical Co., Ltd. are listed as the copolymer having the chemical structure represented by the formula (3).
  • a diallylethylmethylammonium ethylsulfate-maleic acid copolymer represented by the following formula (3-1) eg, 8-3-245 1 manufactured by NITTO BO Medical Co., Ltd.
  • the following formula (3 — 2) The diallyldimethylammonium chloride ⁇ maleic acid copolymer (for example, 8-3-2351 manufactured by NITTO BO Medical Co., Ltd.) and the like can be mentioned.
  • the weight average molecular weight of the copolymer is not particularly limited, and for example, 100
  • the weight average molecular weight of the copolymer having the chemical structure represented by the formula (2) is preferably 150 or more, and more preferably 180 or more. Is particularly preferable. When the weight average molecular weight of the copolymer having the chemical structure represented by the formula (2) is 150,000 or more, desired hydrophilicity is easily exhibited.
  • the solvent contained in the surface treatment agent according to the present embodiment may be any one that allows the reaction product of the fluorine-containing compound and the copolymer to exist (dissolve) in a micelle state.
  • Alcohol solvents with 1 to 5 carbon atoms methanol, ethanol ⁇ 2020/175 121 12 boxes (:171? 2020 /005064
  • the alcohol solvent may contain a slight amount of water, but the alcohol concentration may be 95% by volume or more, and preferably 98% by volume or more. If the alcohol-based solvent contains water in an amount of more than 5% by volume, it may be difficult to allow the reaction product of the fluorine-containing compound and the copolymer to exist (dissolve) in a micelle state. There is.
  • the content ratio (mass basis) of the fluorine-containing compound and the copolymer in the surface treatment agent according to the present embodiment is preferably 1:1 to 25, and 1:2 to 20 It is more preferable that it is present, and it is particularly preferable that it is 1:5 to 15.
  • the content ratio (mass basis) of the fluorine-containing compound and the copolymer is within the above range, more excellent hydrophilicity and oil repellency can be exhibited.
  • the copolymer has the chemical structure represented by the formula (3) (containing a carboxylic acid as a constituent component)
  • the content ratio (mass basis) of the fluorine-containing compound and the copolymer is It is preferably 1:2 or more, and particularly preferably 1:5 to 15.
  • the content ratio (mass standard) is less than 1:2, the desired hydrophilicity may be difficult to be exhibited.
  • the surface treatment agent according to the present embodiment includes both an acid catalyst (eg, hydrochloric acid, acetic acid, phosphoric acid, etc.) and a base catalyst (eg, ammonia water, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, etc.). It is preferably a reaction solution for producing a reaction product of the above-mentioned fluorine-containing compound and the above-mentioned copolymer in a reaction system containing no (catalyst-free condition). When the reaction product is produced in a reaction system containing the catalyst (under acidic condition or alkaline condition), the resulting reaction solution becomes cloudy.
  • an acid catalyst eg, hydrochloric acid, acetic acid, phosphoric acid, etc.
  • a base catalyst eg, ammonia water, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, etc.
  • the reaction solution When the reaction solution is used as a surface treatment agent for a substrate to be treated, the surface of the substrate to be treated may be clouded. Therefore, when the substrate to be treated is a transparent material and is used for applications requiring visibility, if the reaction liquid obtained in the reaction system containing the above catalyst is used as the surface treatment agent, The visibility of the substrate may deteriorate. Therefore, in such a case, the above catalyst should not be included. ⁇ 2020/175 121 13 ⁇ (: 171-1? 2020 /005064
  • reaction solution obtained in a non-reaction system (under non-catalytic conditions) as a surface treatment agent.
  • the surface treatment agent according to the present embodiment described above has excellent hydrophilicity and oil repellency, as will be apparent from Examples described later.
  • the hydrophilicity means, for example, a contact angle meter (for example, a port manufactured by Kyowa Interface Science Co., Ltd. “ ⁇ 1 ⁇ /1 3 3 1 6
  • the contact angle ( 69 ) is measured using "300 (product name) etc.”, it means that the water contact angle is relatively small.
  • the contact angle 9 less than 0 ° water, good Mashiku the 3 0 ° or less, more preferably 0 °.
  • the oil repellency means, for example, a contact angle meter (for example, manufactured by Kyowa Interface Science Co., Ltd.) on the surface of a substrate (glass substrate etc.) which has been surface-treated with the above-mentioned surface treatment agent.
  • a contact angle meter for example, manufactured by Kyowa Interface Science Co., Ltd.
  • the contact angle of dodecane is measured using (product name) etc., it means that the contact angle of dodecane is relatively large.
  • the contact angle of dodecane is 35° or more, preferably 40° or more, more preferably 50° or more.
  • the surface treatment agent of the present embodiment when used for the surface treatment of a substrate to be treated such as glass, plastics, fibers, and building members, an antifouling film or the like is formed on the surface of the substrate to be treated.
  • the functional thin film (surface treatment layer) of can be formed. That is, the surface treatment agent according to this embodiment capable of imparting hydrophilicity and oil repellency can be used as a surface treatment agent for forming an antifouling layer.
  • the surface treatment agent according to the present embodiment can be produced, for example, by mixing the fluorine-containing compound and the copolymer in a solvent under non-catalyst conditions.
  • the mixing ratio of the fluorine-containing compound and the copolymer is, for example, preferably 1 to 25 parts by mass, and 2 to 20 parts by mass with respect to 1 part by mass of the fluorine-containing compound. Is more preferable, and 5 to 15 parts by mass is particularly preferable.
  • the mixing ratio of the fluorine-containing compound and the copolymer is within the above range ⁇ 2020/175 121 14 ⁇ (: 171? 2020 /005064
  • the surface treatment agent obtained can exhibit excellent hydrophilicity and oil repellency.
  • the above-mentioned copolymer has the chemical structure represented by the formula (3) (containing carboxylic acid as a constituent), 1 part by mass of the above-mentioned fluorine-containing compound:
  • It is preferably 1 part by mass or more, and particularly preferably 5 to 15 parts by mass. If the mixing ratio is out of the above range, desired hydrophilicity may not be easily exhibited.
  • the solvent may be any solvent as long as it allows a reaction product of the fluorine-containing compound and the copolymer to exist in a micellar state.
  • an alcohol solvent having 1 to 5 carbon atoms methanol, Ethanol, propanol, butanol, etc.
  • the alcoholic solvent may contain a slight amount of water, but the alcohol concentration may be 95% by volume or more, and preferably 98% by volume or more. If the alcohol-based solvent contains water in an amount of more than 5% by volume, it may be difficult to allow the reaction product of the fluorine-containing compound and the copolymer to exist in a micelle state.
  • the surface treatment method according to the present embodiment includes a step of applying the surface treatment agent according to the present embodiment onto the surface of a substrate to be treated.
  • the method of applying the surface treatment agent to the surface of the substrate to be treated is not particularly limited, and examples thereof include a method of applying using a brush, a mouth roller, a spray, or the like. And the like.
  • the solvent may be removed by heating the coating film formed by applying the surface treatment agent to the surface of the substrate to be treated.
  • the heating method include heating with an oven and heating with a hot press, but are not particularly limited.
  • the heating conditions are, for example, 100 to 180 ° ⁇ and 10 to 60 minutes, preferably 100 to 130 ° ⁇ and 10 to 30 minutes.
  • a surface treatment layer is not formed on the surface (treatment surface) of the substrate to be treated.
  • the surface-treated layer may be formed at least on the surface (first surface) of the base material to be treated, but may be formed on the back surface (second surface). Good.
  • the surface-treated layer can exhibit excellent hydrophilicity and oil repellency.
  • a surface treatment agent was prepared in the same manner as in Sample 1, except that the addition amount of the diallyldimethylammonium chloride ⁇ acrylic amide copolymer was changed to 3009.
  • a surface treatment agent was prepared in the same manner as in Sample 3, except that the addition amount of the diallyldimethylammonium chloride ⁇ acrylic amide copolymer was changed to 3009.
  • a surface treatment agent was prepared in the same manner as in Sample 5, except that the addition amount of the diallyldimethylammonium chloride ⁇ acrylic amide copolymer was changed to 3009.
  • Fluorine-containing compound 200 ⁇ !9 represented by the above formula (5) and diallylethylmethylammoniumethylsulfate-maleic acid copolymer represented by the above formula (3_1) (8 3_245 1, Nittobo Medical Manufactured by the company, weight average molecular weight 30000) 10 And were added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.
  • a surface treatment agent was prepared in the same manner as in Sample 7, except that the addition amount of the diallylethylmethylammoniumethylsulfate ⁇ maleic acid copolymer was changed to 3009.
  • a fluorine-containing compound 20 9 represented by the above formula (5), diallyldimethylammonium Li de maleic acid copolymer represented by the above formula (3_2) (eight 3-235 1, Stevenage toe bow Medical Co., weight average Molecular weight 250 ⁇ 2020/175 121 17 ⁇ (: 171-1? 2020/005064
  • a surface treating agent was prepared in the same manner as in Sample 9 except that the addition amount of the diallyldimethylammonium chloride/maleic acid copolymer was changed to 3009.
  • Ammonia water as basic catalyst A surface treatment agent was prepared in the same manner as in Sample 3.
  • Ammonia water as basic catalyst A surface treatment agent was prepared in the same manner as in Sample 4.
  • Ammonia water as basic catalyst A surface treatment agent was prepared in the same manner as in Sample 7.
  • Ammonia water as basic catalyst A surface treatment agent was prepared in the same manner as in Sample 8.
  • the surface treatment agent (Sample 1) was applied to the first surface of the glass by spin coating (rotation speed: 2000 ", rotation time: 303, drop amount: 0.3 mL). ⁇ 2020/175 121 19 ⁇ (: 171-1? 2020/005064
  • a copolymer of a predetermined fluorine-containing compound, a quaternary ammonium salt of allylamine and an amide compound (diallyldimethylammonium chloride-acrylic represented by the above formula (2 _ 1)
  • a surface treatment agent containing a reaction product with an amide copolymer can impart excellent hydrophilicity and oil repellency. ⁇ 2020/175 121 20 boxes (: 171-1? 2020 /005064
  • the present invention is useful in the technical field of products requiring hydrophilicity and oil repellency.

Abstract

A surface treatment agent capable of providing excellent hydrophilic properties and oil repellency and containing: a fluorine-containing compound indicated by formula (1); a copolymer of a quaternary ammonium salt of arylamine and an amide compound or a carboxylic acid; and a catalyst. In the formula (1), R1 indicates a group containing a fluoroalkyl group, R2 indicates an alkyl group or an alkoxyalkyl group, R3 and R4 each independently indicate a hydrogen atom or a monovalent organic group, x is an integer of 1–100, and y is an integer of 0–100.

Description

\¥02020/175121 1 卩（：17 2020/005064 \¥02020/175121 1 box (: 17 2020/005064
明 細 書 Specification
発明の名称 ： 表面処理剤及びその製造方法、 並びに表面処理方法 技術分野 Title of invention: Surface treatment agent and method for producing the same, and surface treatment method TECHNICAL FIELD
[0001 ] 本発明は、 表面処理剤及びその製造方法、 並びに当該表面処理剤を用いた 表面処理方法に関する。 The present invention relates to a surface treatment agent and a method for producing the same, and a surface treatment method using the surface treatment agent.
背景技術 Background technology
[0002] 産業用機械部品等の生産には、 多種、 多量の油が使用されており、 製造エ 程における部品洗浄や製品洗浄の工程等で排出される含油排水の量も多くな っている。 このような含油排水から油と水とを分離する油水分離技術として 、 例えば、 比重分離等の静置分離技術、 遠心分離技術、 吸着分離技術等が知 られている。 [0002] Various types of large amounts of oil are used in the production of industrial machine parts, etc., and the amount of oil-containing wastewater discharged in the process of parts washing and product washing in the manufacturing process is also large. .. Known oil-water separation technologies for separating oil and water from such oil-containing wastewater include static separation technology such as specific gravity separation, centrifugal separation technology, and adsorption separation technology.
[0003] これらの分離技術のうち、 静置分離技術は多大な時間を要するという問題 があり、 遠心分離技術は大掛かりな装置を必要とするという問題があり、 吸 着分離技術は大量の含油排水の処理に不向きであるという問題がある。 そこ で、 従来、 所定のフッ素化合物と無機化合物とがナノコンポジッ ト化された 複合材料であって、 親水 ·撥油性を有するフッ素含有ナノコンポジッ ト粒子 をろ紙や不織布に担持させた油水分離膜が提案されている （特許文献 1参照 [0003] Among these separation techniques, the static separation technique has a problem that it takes a lot of time, the centrifugal separation technique has a problem that a large-scale device is required, and the adsorption separation technique has a large amount of oil-containing wastewater. There is a problem that it is not suitable for processing. Here, conventionally, a composite material in which a predetermined fluorine compound and an inorganic compound are nanocomposited, and an oil/water separation membrane in which fluorine-containing nanocomposite particles having hydrophilicity/oil repellency are carried on filter paper or nonwoven fabric is used. Proposed (see Patent Document 1)
[0004] 物品表面に付着した油汚れを防止する方法として、 物品表面を、 撥油性を 有する表面処理剤で処理して、 物品表面に防汚膜を形成する方法が知られて いる。 撥油性を有する表面処理剤としては、 ポリテトラフルオロエチレン （ 丁 巳） 、 ポリクロロトリフルオロエチレン等のフッ素樹脂等が広く用い られている。 しかしながら、 フッ素樹脂は高い撥水性を有するため、 物品表 面に付着した油汚れを水洗浄により洗い流すことが困難である。 そのため、 油汚れを防止するための撥油性と、 付着した油汚れを水洗浄するための親水 性とを有する表面処理剤の提案が望まれている。 [0004] As a method for preventing oil stains attached to the surface of an article, a method is known in which the article surface is treated with a surface-treating agent having oil repellency to form an antifouling film on the article surface. As a surface treatment agent having oil repellency, fluororesins such as polytetrafluoroethylene (Temono) and polychlorotrifluoroethylene are widely used. However, since fluororesins have high water repellency, it is difficult to wash away oil stains attached to the surface of articles by washing with water. Therefore, it is desired to propose a surface treatment agent having oil repellency for preventing oil stains and hydrophilicity for washing adhered oil stains with water.
[0005] 従来、 表面処理剤に含まれる親水性及び撥油性を有する樹脂組成物として 〇 2020/175121 2 卩(：171? 2020 /005064 [0005] Conventionally, as a resin composition having hydrophilicity and oil repellency contained in a surface treatment agent 〇 2020/175 121 2 卩(: 171-1? 2020/005064
、 炭素数 1 〜 1 8のペルフルオロアルキル （メタ） アクリル酸エステルと親 水基含有モノマーとを構成成分に含む共重合体が知られている （特許文献 2 参照） 。 A copolymer containing a perfluoroalkyl (meth)acrylic acid ester having 1 to 18 carbon atoms and a hydrophilic group-containing monomer as constituent components is known (see Patent Document 2).
先行技術文献 Prior art documents
特許文献 Patent literature
[0006] 特許文献 1 :特開 2 0 1 5 _ 1 8 7 2 2 0号公報 Patent Document 1: Japanese Patent Laid-Open No. 20 1 5 _ 1 8 7 2 20
特許文献 2 :特開 2 0 0 8— 2 9 7 4 8 2号公報 Patent Document 2: Japanese Unexamined Patent Publication No. 2 0 0 8 — 2 9 7 4 8 2
発明の概要 Summary of the invention
発明が解決しようとする課題 Problems to be Solved by the Invention
[0007] 上記特許文献 1 に記載されている油水分離技術や上記特許文献 2に記載さ れている防汚膜を形成するための表面処理剤等の技術分野においては、 優れ た親水性及び撥油性を有する材料が必須であり、 当該親水性及び撥油性をさ らに向上させてなる材料の提案に対する要望が高まっている。 [0007] In the technical fields such as the oil-water separation technology described in Patent Document 1 and the surface treatment agent for forming an antifouling film described in Patent Document 2 described above, excellent hydrophilicity and repellency are exhibited. A material having oiliness is indispensable, and there is an increasing demand for proposals of materials having further improved hydrophilicity and oil repellency.
[0008] 上記課題に鑑みて、 本発明は、 優れた親水性及び撥油性を付与可能な表面 処理剤及びその製造方法、 優れた親水性及び撥油性を発現可能な表面処理基 材、 並びに被処理基材の表面に優れた親水性及び撥油性を付与可能な表面処 理方法を提供することを目的とする。 In view of the above problems, the present invention provides a surface treatment agent capable of imparting excellent hydrophilicity and oil repellency, a method for producing the same, a surface treatment base material capable of exhibiting excellent hydrophilicity and oil repellency, and an object to be treated. It is an object of the present invention to provide a surface treatment method capable of imparting excellent hydrophilicity and oil repellency to the surface of a treated substrate.
課題を解決するための手段 Means for solving the problem
[0009] 上記課題を解決するために、 本発明は、 下記式 （1） で示されるフッ素含 有化合物と、 アリルアミンの 4級アンモニウム塩及びアミ ド化合物又はカル ボン酸の共重合体と、 溶媒とを含有することを特徴とする表面処理剤を提供 する。 In order to solve the above problems, the present invention provides a fluorine-containing compound represented by the following formula (1), a quaternary ammonium salt of allylamine and a copolymer of an amide compound or carboxylic acid, and a solvent. There is provided a surface treatment agent comprising:
[0010] [化 1 ] [0010] [Chemical 1]
Figure imgf000004_0001
Figure imgf000004_0001
上記式 （1） 中、 はフルオロアルキル基を含有する基を表し、 はアル 〇 2020/175121 3 卩（：171? 2020 /005064 In the above formula (1), represents a group containing a fluoroalkyl group, 〇 2020/175 121 3 卩 (: 171-1? 2020 /005064
キル基又はアルコキシアルキル基を表し、 及び は各々独立して水素原子 又は 1価の有機基を表し、 Xは 1〜 1 0 0の整数であり、 Vは〇〜 1 0 0の 整数である。 Represents a kill group or an alkoxyalkyl group, and each independently represents a hydrogen atom or a monovalent organic group, X is an integer of 1 to 100, and V is an integer of 0 to 100.
[001 1 ] 前記共重合体は、 下記式 （2） で示される化学構造を有するものであって もよいし、 下記式 （3） で示される化学構造を有するものであってもよく、 前記フッ素含有化合物と前記共重合体との含有比 （質量基準） が、 1 : 1〜 [001 1] The copolymer may have a chemical structure represented by the following formula (2), or may have a chemical structure represented by the following formula (3): The content ratio (mass basis) of the fluorine-containing compound and the copolymer is 1:1 to
2 5であればよく、 前記溶媒が、 炭素数 1〜 5のアルコール系溶媒であれば よい。 25 may be sufficient, and the solvent may be an alcohol solvent having 1 to 5 carbon atoms.
[0012] [化 2] [0012] [Chemical 2]
Figure imgf000005_0003
Figure imgf000005_0003
上記式 （2） 中、 ’ 及び尺 2’ は各々独立して炭素数 1〜 4のアルキル基 を表し、 X-はハロゲン化物イオン、 無機アニオン又は有機アニオンを表す。 In the above formula (2), 'and rod 2' represents an alkyl group having 1-4 carbon atoms each independently, X- represents a halide ion, an inorganic anion or an organic anion.
[0013] [化 3] [0013] [Chemical Formula 3]
Figure imgf000005_0001
Figure imgf000005_0001
上記式 （3） 中、
Figure imgf000005_0002
は各々独立して炭素数 1〜 4のアルキル基 を表し、 X-はハロゲン化物イオン、 無機アニオン又は有機アニオンを表す。 In the above formula (3),
Figure imgf000005_0002
Each independently represents an alkyl group having 1 to 4 carbon atoms, and X- represents a halide ion, an inorganic anion or an organic anion.
[0014] 前記式 （1） において、 ソが 0であればよく、 で表されるフルオロアル キル基を含有する基が、 下記式 （4） で表される基であればよく、 はメチ ル基であればよく、 Xが 1〜 1 0の整数であればよい。 〇 2020/175121 4 卩（：171? 2020 /005064 [0014] In the above formula (1), it suffices that so is 0, and the group containing a fluoroalkyl group represented by is a group represented by the following formula (4): Any group may be used, and X may be an integer of 1 to 10. 〇 2020/175 121 4 卩 (: 171? 2020 /005064
[0015] [化 4] [0015] [Chemical 4]
—〇 〇 3)[0〇 2〇 〇 3)](50〇^7 (4) — 〇 〇 3 ) [0 〇 2 〇 〇 3 )] (5 0 〇 ^ 7 (4)
上記式 ( 4 ) 中、 は〇〜 2の整数である。 In the above formula (4), is an integer from 0 to 2.
[0016] 本発明は、 第 1面及び当該第 1面に対向する第 2面を有する基部と、 前記 基部の少なくとも前記第 1面に設けられてなる表面処理層とを備え、 前記表 面処理層は、 上記表面処理剤を用いた表面処理が前記基部の前記第 1面に施 されることにより形成されてなるものであることを特徴とする表面処理基材 を提供する。 [0016] The present invention comprises a base having a first surface and a second surface facing the first surface, and a surface treatment layer provided on at least the first surface of the base, wherein the surface treatment is performed. The layer provides a surface-treated base material, which is formed by subjecting the first surface of the base to a surface treatment using the surface-treating agent.
[0017] 本発明は、 下記式 ( 1 ) で示されるフッ素含有化合物と、 アリルアミンの 4級アンモニウム塩及びアミ ド化合物又はカルボン酸の共重合体と、 溶媒と を混合することを特徴とする表面処理剤の製造方法を提供する。 かかる製造 方法において、 酸触媒及びアルカリ触媒のいずれをも混合させないのが好ま しい。 The present invention is characterized by mixing a fluorine-containing compound represented by the following formula (1), a copolymer of quaternary ammonium salt of allylamine and an amide compound or carboxylic acid, and a solvent: A method for producing a treating agent is provided. In such a production method, it is preferable that neither an acid catalyst nor an alkali catalyst is mixed.
[0018] [化 5] [0018] [Chemical 5]
Figure imgf000006_0002
上記式 ( 1 ) 中、 はフルオロアルキル基を含有する基を表し、 はアル キル基又はアルコキシアルキル基を表し、
Figure imgf000006_0001
及び は各々独立して水素原子 又は 1価の有機基を表し、 Xは 1〜 1 0 0の整数であり、 Vは〇〜 1 0 0の 整数である。
Figure imgf000006_0002
In the formula (1), represents a group containing a fluoroalkyl group, represents an alkyl group or an alkoxyalkyl group,
Figure imgf000006_0001
And each independently represent a hydrogen atom or a monovalent organic group, X is an integer of 1 to 100, and V is an integer of 0 to 100.
[0019] 本発明は、 上記表面処理剤を用いて被処理基材に表面処理を施すことを特 徴とする表面処理方法を提供する。 [0019] The present invention provides a surface treatment method characterized by subjecting a substrate to be treated to a surface treatment using the above-mentioned surface treatment agent.
発明の効果 Effect of the invention
[0020] 本発明によれば、 優れた親水性及び撥油性を付与可能な表面処理剤及びそ の製造方法、 優れた親水性及び撥油性を発現可能な表面処理基材、 並びに被 処理基材の表面に優れた親水性及び撥油性を付与可能な表面処理方法を提供 〇 2020/175121 5 卩（：171? 2020 /005064 [0020] According to the present invention, a surface treatment agent capable of imparting excellent hydrophilicity and oil repellency, a method for producing the same, a surface treated substrate capable of exhibiting excellent hydrophilicity and oil repellency, and a treated substrate Provide a surface treatment method that can impart excellent hydrophilicity and oil repellency to the surface of 〇 2020/175 121 5 boxes (: 171-1? 2020 /005064
することができる。 can do.
発明を実施するための形態 MODE FOR CARRYING OUT THE INVENTION
［0021］ 本発明の実施の形態について説明する。 [0021] An embodiment of the present invention will be described.
［表面処理剤］ [Surface treatment]
本実施形態に係る表面処理剤は、 下記式 （1） で示されるフッ素含有化合 物と、 アリルアミンの 4級アンモニウム塩及びアミ ド化合物又はカルボン酸 の共重合体と、 溶媒とを含有する。 かかる表面処理剤は、 上記フッ素含有化 合物と上記共重合体との反応生成物をミセル状態で含むものであつて、 当該 ミセル状の反応生成物を製造するときの反応溶液として調製され得る。 The surface treatment agent according to the present embodiment contains a fluorine-containing compound represented by the following formula (1), a quaternary ammonium salt of allylamine and a copolymer of an amide compound or a carboxylic acid, and a solvent. Such a surface treatment agent contains a reaction product of the above-mentioned fluorine-containing compound and the above-mentioned copolymer in a micelle state, and can be prepared as a reaction solution when producing the micelle-like reaction product. ..
[0022] [化 6] [0022] [Chemical 6]
Figure imgf000007_0001
Figure imgf000007_0001
式 （1） 中、 はフルオロアルキル基を含有する基を表し、 はアルキル 基又はアルコキシアルキル基を表し、
Figure imgf000007_0002
は各々独立して水素原子又は 1価の有機基を表し、 Xは 1〜 1 0 0の整数であり、 Vは〇〜 1 0 0の整数 である。 In formula (1), represents a group containing a fluoroalkyl group, represents an alkyl group or an alkoxyalkyl group,
Figure imgf000007_0002
Each independently represent a hydrogen atom or a monovalent organic group, X is an integer of 1 to 100, and V is an integer of 0 to 100.
［0023］ 式 （1） において、 で表されるフルオロアルキル基を含有する基として は、 例えば、 一〇 3、 一〇2 5、 一〇3 7、
Figure imgf000007_0003
In [0023] formula (1), in the group having a fluoroalkyl group represented, for example, ten 3, ten 2 5, ten 3 7,
Figure imgf000007_0003
（ = 1〜 1 0） で表されるフルオロアルキル基；オキシフルオロアルキレ ン基等を挙げることができ、 これらのうち、 下記式 （4） で示されるオキシ フルオロアルキレン基であるのが好ましい。 Examples thereof include a fluoroalkyl group represented by (= 1 to 10); an oxyfluoroalkylen group, and the like, and among these, an oxyfluoroalkylene group represented by the following formula (4) is preferable.
［0024］ ［化 7］ [0024] [Chemical 7]
—〇 〇 3）［0〇 2〇 〇 3）］（50〇^7 （4） — 〇 〇 3 ) [0 〇 2 〇 〇 3 )] ( 5 〇 ^ 7 (4)
式 （4） 中、 は〇〜 2の整数である。 In formula (4), is an integer from 0 to 2.
［0025］ 式 （1） において、
Figure imgf000007_0004
で表されるアルキル基としては、 例えば、 メチル基 、 エチル基等の炭素数 1〜 2のアルキル基が挙げられ、
Figure imgf000007_0005
で表されるアルコ \¥02020/175121 6 卩（：17 2020/005064 [0025] In equation (1),
Figure imgf000007_0004
The alkyl group represented by, for example, a methyl group, an alkyl group having 1 to 2 carbon atoms such as an ethyl group,
Figure imgf000007_0005
Arco represented by \¥02020/175 121 6 (: 17 2020/005064
キシアルキル基としては、 例えば、 メ トキシメチル基、 メ トキシエチル基、 エトキシメチル基、 エトキシエチル基等の炭素数 2〜 4のアルコキシアルキ ル基が挙げられる。 これらのうち、 で表される基としては、 アルキル基が 好ましく、 メチル基が特に好ましい。 Examples of the xyalkyl group include alkoxyalkyl groups having 2 to 4 carbon atoms such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group and an ethoxyethyl group. Among these, the group represented by is preferably an alkyl group, and particularly preferably a methyl group.
［0026］ 式 （1） において、
Figure imgf000008_0001
及び で表される有機基としては、 例えば、 下記式 （）） 〜 （▽） で示される基を挙げることができる。 [0026] In equation (1),
Figure imgf000008_0001
Examples of the organic groups represented by and include groups represented by the following formulas ()) to (∇).
[0027] [化 8] [0027] [Chemical 8]
-〇13 …⑴ -〇 1 3 …⑴
-COOH ---（||） -COOH --- (||)
— C〇0（CH2）2〇H （ ） — C 〇 0 (CH 2 ) 2 〇 H ()
— 00— 1^1（（^3）2 （IV）
Figure imgf000008_0002
— 00— 1^1 ((^3)2 (IV)
Figure imgf000008_0002
［0028］ 式 （1） において、 トリアルコキシシリル基又はトリアルコキシアルコキ シシリル基 （一 3 I （〇［¾ 2）3） が結合する中間鎖 （一 C H 2- C H -） の数父は 、 1〜 1 0 0であり、 好ましくは 1〜 5 0、 より好ましくは 1〜 1 0、 特に 好ましくは 2〜 5である。 また、 中間鎖 （一〇
Figure imgf000008_0003
の数ソは、 0 〜 1 0 0であり、 好ましくは〇〜 5 0、 より好ましくは〇〜 1 0である。[0028] In formula (1), the number of the intermediate chain (one CH 2 -CH -) to which the trialkoxysilyl group or trialkoxyalkoxysilyl group (1 3 I (○[¾ 2 ) 3 ) is bonded is It is 1 to 100, preferably 1 to 50, more preferably 1 to 10 and particularly preferably 2 to 5. In addition, the middle chain (10
Figure imgf000008_0003
The number of s is 0 to 100, preferably 0 to 50, and more preferably 0 to 10.
［0029］ 上記フッ素含有化合物として好適な化合物としては、 下記式 （5） 〜 （9 ） で示される化合物を例示することができる。 特に、 上記フッ素含有化合物 が式 （5） 又は式 （8） で示される化合物 （式 （1） においてソ= 0である 化合物） であると、 1分子中に占められるフッ素原子の割合が大きいことで 、 本実施形態に係るナノコンポジッ ト粒子を生成する反応を効率的に進行さ せることができる。 [0029] Examples of compounds suitable as the fluorine-containing compound include compounds represented by the following formulas (5) to (9). In particular, when the above-mentioned fluorine-containing compound is a compound represented by formula (5) or formula (8) (a compound in which so=0 in formula (1)), the proportion of fluorine atoms occupied in one molecule is large. Thus, the reaction for producing the nanocomposite particles according to the present embodiment can be efficiently advanced.
[0030] 〇 2020/175121 7 卩(：171? 2020 /005064 [0030] 〇 2020/175 121 7 卩(: 171? 2020/005064
[化 9] ⑸
Figure imgf000009_0001
[Chemical 9] ⑸
Figure imgf000009_0001
式 （5） 中、 X’ は 2又は 3である。 In the formula (5), X′ is 2 or 3.
[0031] [化 10] ⑹ [0031] [Chemical 10] ⑹
Figure imgf000009_0002
Figure imgf000009_0002
[0032] [化 11] [0032] [Chemical 11]
Figure imgf000009_0003
Figure imgf000009_0003
式 （6） 及び式 （7） 中、 は、 一〇 （〇 3）〇〇 2〇 （〇 3）〇〇3 7 で表される基である。 式 （6） 中、 X 3は 1 〜 1 00の整数である。 式 （7 ） 中、 X匕は 1 〜 1 00の整数であり、 ソ匕は 1 〜 500の整数である。 Equation (6) and the formula (7), is ten (〇 3) hundred 2 〇 (〇 3) a group represented by the hundred 3 7. In the formula (6), X 3 is an integer of 1 to 100. In the formula (7), X-shallow is an integer of 1 to 100 and Suk-oh is an integer of 1 to 500.
[0033] [化 12] [0033] [Chemical 12]
Figure imgf000009_0005
Figure imgf000009_0005
式 （8） 中、 X〇は 1 〜 1 0の整数であり、 ソ〇は〇〜 1 00の整数であ る。 In formula (8), X 〇 is an integer from 1 to 10 and so 〇 is an integer from 〇 to 100.
[0034] [化 13] [0034] [Chemical 13]
Figure imgf000009_0004
〇 2020/175121 8 卩(：171? 2020 /005064
Figure imgf000009_0004
〇 2020/175 121 8 卩 (: 171? 2020 /005064
式 （9） 中、 X は 1〜 1 0の整数であり、 V は〇〜 1 0 0の整数であ る。 In formula (9), X is an integer of 1 to 10 and V is an integer of 0 to 100.
[0035] 上記式 （1） で示されるフッ素含有化合物は、 下記式 （丨 3） で示される フッ素含有過酸化物の存在下に、 下記式 （丨 匕） で示される単量体と、 下記 式 （ I 〇） で示される単童体とを重合させることにより得られる。 なお、 こ の反応生成物 （フッ素含有化合物） 中には、 フルオロアルキル基を含有する 基 （ ） が片末端のみに導入されているオリゴマーが任意の割合で含まれて いてもよい。 [0035] The fluorine-containing compound represented by the above formula (1) is obtained by reacting a monomer represented by the following formula () with a monomer represented by the following formula in the presence of a fluorine-containing peroxide represented by the following formula (3). It is obtained by polymerizing with a single body of the formula (I 0 ). The reaction product (fluorine-containing compound) may contain an oligomer in which the group () containing a fluoroalkyl group is introduced only at one end, at an arbitrary ratio.
[0036] [化 14] [0036] [Chemical 14]
Figure imgf000010_0001
式 （ I 3） 〜 （ I 〇） 中、 はフルオロアルキル基を含有する基を表し、 はアルキル基又はアルコキシアルキル基を表し、 及び は各々独立して 水素原子又は 1価の有機基を表す。
Figure imgf000010_0001
In formulas (I 3) to (I 0 ), represents a group containing a fluoroalkyl group, represents an alkyl group or an alkoxyalkyl group, and represents each independently a hydrogen atom or a monovalent organic group.
[0037] 本実施形態に係る表面処理剤は、 アリルアミンの 4級アンモニウム塩とア ミ ド化合物との共重合体、 又はアリルアミンの 4級アンモニウム塩とカルボ ン酸との共重合体を含む。 これらの共重合体の構成成分であるアリルアミン の 4級アンモニウム塩としては、 例えば、 ジアリルジアルキルアンモニウム クロリ ド、 ジアリルジアルキルアンモニウムアルキルサルフェイ ト、 ジアリ ルジアルキルアンモニウムヒドロキシド、 ジアリルジアルキルアンモニウム フルオリ ド等が挙げられる。 ジアリルジアルキルアンモニウムクロリ ドとし ては、 例えば、 ジアリルジメチルアンモニウムクロリ ド、 ジアリルェチルメ チルアンモニウムクロリ ド、 ジアリルジェチルアンモニウムクロリ ド等が挙 〇 2020/175121 9 卩（：171? 2020 /005064 The surface treatment agent according to the present embodiment contains a copolymer of a quaternary ammonium salt of allylamine and an amide compound, or a copolymer of a quaternary ammonium salt of allylamine and carboxylic acid. Examples of the quaternary ammonium salt of allylamine, which is a constituent of these copolymers, include diallyldialkylammonium chloride, diallyldialkylammonium alkylsulfate, diallyldialkylammonium hydroxide, diallyldialkylammonium fluoride and the like. To be Examples of diallyldialkylammonium chlorides include diallyldimethylammonium chloride, diallylethylmethylammonium chloride, diallylethylylammonium chloride and the like. 〇 2020/175 121 9 (:171? 2020/005064
げられる。 ジアリルアルキルアンモニウムアルキルサルフェイ トとしては、 例えば、 ジアリルジメチルアンモニウムメチルサルフェイ ト、 ジアリルェチ ルメチルアンモニウムメチルサルフェイ ト、 ジアリルジェチルアンモニウム メチルサルフェイ ト、 ジアリルジメチルアンモニウムェチルサルフェイ ト、 ジアリルェチルメチルアンモニウムェチルサルフェイ ト、 ジアリルジェチル アンモニウムェチルサルフェイ ト等が挙げられる。 ジアリルジアルキルアン モニウムヒドロキシドとしては、 例えば、 ジアリルジメチルアンモニウムヒ ロドキシド、 ジアリルェチルメチルアンモニウムヒドロキシド、 ジアリルジ ェチルアンモニウムヒドロキシド等が挙げられる。 ジアリルジアルキルアン モニウムフルオリ ドとしては、 ジアリルジメチルアンモニウムフルオリ ド、 ジアリルェチルメチルアンモニウムフルオリ ド、 ジアリルジェチルアンモニ ウムフルオリ ド等が挙げられる。 You can get it. Examples of diallylalkylammonium alkylsulfates include diallyldimethylammonium methylsulfate, diallylmethylammonium methylsulfate, diallylditylammonium methylsulfate, diallyldimethylammoniumethylsulfate, diallylethyl. Examples include methylammonium ethyl sulfate and diallyl tylethyl ammonium ethyl sulfate. Examples of diallyldialkylammonium hydroxide include diallyldimethylammonium hydroxide, diallylethylmethylammonium hydroxide, diallyldiethylammonium hydroxide and the like. Examples of diallyldialkylammonium fluoride include diallyldimethylammonium fluoride, diallylethylammonium fluoride, diallyljetylammonium fluoride and the like.
[0038] 上記共重合体の構成成分であるアミ ド化合物としては、 例えば、 アクリル アミ ド、 アルキルアクリルアミ ド、 ジアルキルアクリルアミ ド、 アミノアル キルアクリルアミ ド、 ヒドロキシアルキルアクリルアミ ド等が挙げられ、 力 ルボン酸としては、 例えば、 アクリル酸、 メタクリル酸等のモノカルボン酸 ;マレイン酸、 フマル酸等のジカルボン酸等が挙げられる。 [0038] Examples of the amide compound that is a constituent component of the above-mentioned copolymer include acrylic amide, alkyl acrylate, dialkyl acrylate, aminoalkyl acrylate, hydroxyalkyl acrylate, and the like. Examples of the carboxylic acid include monocarboxylic acids such as acrylic acid and methacrylic acid; dicarboxylic acids such as maleic acid and fumaric acid.
[0039] 上記共重合体としては、 例えば、 下記式 （2） 又は下記式 （3） で示され る化学構造を有するもの等が挙げられ、 八3 -」一4 1、 八3 -」一8 1、 ？八3 -」一8 1 1_、 八3 - 2 3 5 1、 八3 - 2 4 5 1等の市販品 （いずれも製品名， ニッ トーボーメディカル社製） を用いてもよい。 [0039] Examples of the above-mentioned copolymer include those having a chemical structure represented by the following formula (2) or the following formula (3), and the like: 8 3 -" 1 4 1, 8 3 -" 1 8 1,? Commercially available products such as 8 3 -" 1 8 1 1_, 8 3 -2 3 5 1, 8 3 -2 4 5 1 (all product names, manufactured by Nittobo Medical Co., Ltd.) may be used.
[0040] [化 15] [0040] [Chemical 15]
Figure imgf000011_0001
Figure imgf000011_0001
式 （2） 中、 ’ 及び V， は各々独立して炭素数 1〜 4のアルキル基を表 \¥02020/175121 10 卩(：17 2020/005064 In formula (2),'and V, each independently represent an alkyl group having 1 to 4 carbon atoms. \¥02020/175 121 10 卩(: 17 2020/005064
し、 X-はハロゲン化物イオン、 無機アニオン又は有機アニオンを表す。 X- represents a halide ion, an inorganic anion or an organic anion.
[0041] [化 16] [0041] [Chemical 16]
Figure imgf000012_0001
Figure imgf000012_0001
式 （3） 中、 及び は各々独立して炭素数 1〜 4のアルキル基を表 し、 X-はハロゲン化物イオン、 無機アニオン又は有機アニオンを表す。 In formula (3), and each independently represent an alkyl group having 1 to 4 carbon atoms, and X − represents a halide ion, an inorganic anion or an organic anion.
[0042] 式 （2） 及び式 （3） において、
Figure imgf000012_0002
及び [¾4’ で表 されるアルキル基としては、 例えば、 メチル基、 エチル基、 プロピル基、 イ ソプロピル基、 プチル基等の炭素数 1〜 4のアルキル基が挙げられる。 式 （ 2） 及び式 （3） において、 X-で表されるハロゲン化物イオンとしては、 例 えば、 フッ化物イオン （ _） 、 塩化物イオン （〇 卜） 等が挙げられ、 無機ア ニオンとしては、 例えば、 水酸化物イオン （〇 1~1 _） 、 硫酸水素イオン （ 1~13 〇 4_） 、 硝酸イオン （1\1〇3-） 等が挙げられ、 有機アニオンとしては、 例えば 、 メチル硫酸イオン （〇1~133〇4-） 等のアルキル硫酸イオン、 酢酸イオン （〇 1~13〇〇〇-） 等が挙げられる。 [0042] In equation (2) and equation (3),
Figure imgf000012_0002
Examples of the alkyl group represented by [4′] include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. In the formulas (2) and (3), examples of the halide ion represented by X- include a fluoride ion (_), a chloride ion (○), and the like. , For example, hydroxide ion (〇 1 to 1 _), hydrogen sulfate ion (1 to 13 〇 4 _), nitrate ion (1\10 〇 3- ), and the like, and the organic anion includes, for example, methyl. sulfate ion (Rei_1 ~ 1 3 3_Rei 4) alkyl sulfate ion such as acetate ion (〇 1-1 3 〇_〇_〇-) and the like.
[0043] 式 （2） で示される化学構造を有する共重合体としては、 例えば、 下記式 （2 - 1） で示されるジアリルジメチルアンモニウムクロリ ド · アクリルア ミ ド共重合体 （例えば、 ニッ トーボーメディカル社製の 八3_」一4 1、 八3-」一81、 ？八3-」一81 1_等） 等が挙げられ、 式 （3） で示さ れる化学構造を有する共重合体としては、 例えば、 下記式 （3— 1） で示さ れるジアリルエチルメチルアンモニウムエチルサルフェイ ト ·マレイン酸共 重合体 （例えば、 ニッ トーボーメディカル社製の 八3-245 1等） 、 下 記式 （3— 2） で示されるジアリルジメチルアンモニウムクロリ ド ·マレイ ン酸共重合体 （例えば、 ニッ トーボーメディカル社製の 八3-235 1等 ） 等が挙げられる。 \¥0 2020/175121 1 1 20201005064 Examples of the copolymer having the chemical structure represented by the formula (2) include, for example, diallyldimethylammonium chloride·acrylic amide copolymer represented by the following formula (2-1) (for example, Nitovo 8-3_" 41 1, 8 3-" 81, ?8 3-" 81 1_, etc. manufactured by Medical Co., Ltd. are listed as the copolymer having the chemical structure represented by the formula (3). , For example, a diallylethylmethylammonium ethylsulfate-maleic acid copolymer represented by the following formula (3-1) (eg, 8-3-245 1 manufactured by NITTO BO Medical Co., Ltd.), the following formula (3 — 2) The diallyldimethylammonium chloride·maleic acid copolymer (for example, 8-3-2351 manufactured by NITTO BO Medical Co., Ltd.) and the like can be mentioned. \\0 2020/175 121 1 1 20201005064
[0044] [化 17] [0044] [Chemical 17]
2 2
0=0 2 1 0=0 21
©/ 〇 ©/〇
N ..¼ '|〇1 N .. ¼' | 〇 1
3 3
[0045] [化 18] [0045] [Chemical 18]
Figure imgf000013_0001
Figure imgf000013_0001
[0047] 共重合体の重量平均分子量は特に限定されるものではなく、 例えば 1 0 0 [0047] The weight average molecular weight of the copolymer is not particularly limited, and for example, 100
0 0以上であればよいが、 式 （2） で示される化学構造を有する共重合体の 重量平均分子量は 1 5 0 0 0 0以上であるのが好ましく、 1 8 0 0 0 0以上 であるのが特に好ましい。 式 （2） で示される化学構造を有する共重合体の 重量平均分子量が 1 5 0 0 0 0以上であることで、 所望とする親水性が発現 されやすくなる。 The weight average molecular weight of the copolymer having the chemical structure represented by the formula (2) is preferably 150 or more, and more preferably 180 or more. Is particularly preferable. When the weight average molecular weight of the copolymer having the chemical structure represented by the formula (2) is 150,000 or more, desired hydrophilicity is easily exhibited.
[0048] 本実施形態に係る表面処理剤に含有される溶媒は、 上記フッ素含有化合物 と上記共重合体との反応生成物をミセル状態で存在 （溶解） させ得るもので あればよく、 例えば、 炭素数 1〜 5のアルコール系溶媒 （メタノール、 エタ 〇 2020/175121 12 卩（：171? 2020 /005064 [0048] The solvent contained in the surface treatment agent according to the present embodiment may be any one that allows the reaction product of the fluorine-containing compound and the copolymer to exist (dissolve) in a micelle state. Alcohol solvents with 1 to 5 carbon atoms (methanol, ethanol 〇 2020/175 121 12 boxes (：171? 2020 /005064
ノ _ル、 プロパノール、 ブタノール等） であればよく、 炭素数 4以上のアル コール系溶媒が用いられる場合には、 ノルマルアルコールであるのが好まし い。 かかるアルコール系溶媒は僅かに水を含んでいてもよいが、 アルコール 濃度が 9 5容量％以上であればよく、 9 8容量％以上であるのが好ましい。 かかるアルコール系溶媒に水が 5容量％を超えて含まれていると、 上記フッ 素含有化合物と上記共重合体との反応生成物をミセル状態で存在 （溶解） さ せることが困難となるおそれがある。 Nol, propanol, butanol, etc.), and when an alcohol solvent having 4 or more carbon atoms is used, it is preferably normal alcohol. The alcohol solvent may contain a slight amount of water, but the alcohol concentration may be 95% by volume or more, and preferably 98% by volume or more. If the alcohol-based solvent contains water in an amount of more than 5% by volume, it may be difficult to allow the reaction product of the fluorine-containing compound and the copolymer to exist (dissolve) in a micelle state. There is.
[0049] 本実施形態に係る表面処理剤における上記フッ素含有化合物と上記共重合 体との含有比 （質量基準） は、 1 : 1〜 2 5であるのが好ましく、 1 : 2〜 2 0であるのがより好ましく、 1 : 5〜 1 5であるのが特に好ましい。 上記 フッ素含有化合物と上記共重合体との含有比 （質量基準） が上記範囲内にあ ることで、 より優れた親水性及び撥油性が発現され得る。 上記共重合体が式 （3） で示される化学構造を有するもの （構成成分としてカルボン酸を含む もの） である場合、 上記フッ素含有化合物と上記共重合体との含有比 （質量 基準） は、 1 : 2以上であるのが好ましく、 1 : 5〜 1 5であるのが特に好 ましい。 当該含有比 （質量基準） が 1 : 2未満であると、 所望とする親水性 が発現され難くなるおそれがある。 [0049] The content ratio (mass basis) of the fluorine-containing compound and the copolymer in the surface treatment agent according to the present embodiment is preferably 1:1 to 25, and 1:2 to 20 It is more preferable that it is present, and it is particularly preferable that it is 1:5 to 15. When the content ratio (mass basis) of the fluorine-containing compound and the copolymer is within the above range, more excellent hydrophilicity and oil repellency can be exhibited. When the copolymer has the chemical structure represented by the formula (3) (containing a carboxylic acid as a constituent component), the content ratio (mass basis) of the fluorine-containing compound and the copolymer is It is preferably 1:2 or more, and particularly preferably 1:5 to 15. When the content ratio (mass standard) is less than 1:2, the desired hydrophilicity may be difficult to be exhibited.
[0050] 本実施形態に係る表面処理剤は、 酸触媒 （例えば、 塩酸、 酢酸、 リン酸等 ） 及び塩基触媒 （例えば、 アンモニア水、 水酸化ナトリウム水溶液、 水酸化 カリウム水溶液等） のいずれをも含まない反応系 （無触媒条件下） で上記フ ッ素含有化合物と上記共重合体との反応生成物を製造するときの反応溶液で あるのが好ましい。 上記触媒を含む反応系 （酸性条件下又はアルカリ性条件 下） で上記反応生成物を製造すると、 得られる反応溶液が白濁してしまう。 当該反応溶液を被処理基材の表面処理剤として用いると、 被処理基材の表面 が白濁するおそれがある。 そのため、 被処理基材が透明材料であって、 視認 性を必要とする用途に用いられるものである場合、 上記触媒を含む反応系で 得られる反応用液を表面処理剤として用いると、 被処理基材の視認性が劣化 してしまうおそれがある。 よって、 このような場合には、 上記触媒を含まな 〇 2020/175121 13 卩（：171? 2020 /005064 [0050] The surface treatment agent according to the present embodiment includes both an acid catalyst (eg, hydrochloric acid, acetic acid, phosphoric acid, etc.) and a base catalyst (eg, ammonia water, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, etc.). It is preferably a reaction solution for producing a reaction product of the above-mentioned fluorine-containing compound and the above-mentioned copolymer in a reaction system containing no (catalyst-free condition). When the reaction product is produced in a reaction system containing the catalyst (under acidic condition or alkaline condition), the resulting reaction solution becomes cloudy. When the reaction solution is used as a surface treatment agent for a substrate to be treated, the surface of the substrate to be treated may be clouded. Therefore, when the substrate to be treated is a transparent material and is used for applications requiring visibility, if the reaction liquid obtained in the reaction system containing the above catalyst is used as the surface treatment agent, The visibility of the substrate may deteriorate. Therefore, in such a case, the above catalyst should not be included. 〇 2020/175 121 13 卩 (: 171-1? 2020 /005064
い反応系 （無触媒条件下） で得られる反応溶液を表面処理剤として用いるの が好ましい。 It is preferable to use a reaction solution obtained in a non-reaction system (under non-catalytic conditions) as a surface treatment agent.
[0051 ] 上述した本実施形態に係る表面処理剤は、 後述する実施例からも明らかな ように、 優れた親水性と撥油性とを有する。 ここで、 親水性とは、 例えば、 上記表面処理剤により表面処理が施された基材 （ガラス基材等） の表面につ いて接触角計 （例えば、 協和界面科学社製の口 「〇 1\/1 3 3 1 6 「 3 0 0 （ 製品名） 等） を用いて水の接触角 （ 6 9） を測定したとき、 水の接触角が 相対的に小さいことを意味する。 具体的には、 水の接触角が 9 0 ° 未満、 好 ましくは 3 0 ° 以下、 より好ましくは 0 ° である。 The surface treatment agent according to the present embodiment described above has excellent hydrophilicity and oil repellency, as will be apparent from Examples described later. Here, the hydrophilicity means, for example, a contact angle meter (for example, a port manufactured by Kyowa Interface Science Co., Ltd. “○ 1 \/1 3 3 1 6 When the water contact angle ( 69 ) is measured using "300 (product name) etc.", it means that the water contact angle is relatively small. the contact angle 9 less than 0 ° water, good Mashiku the 3 0 ° or less, more preferably 0 °.
[0052] また、 撥油性とは、 例えば、 上記表面処理剤により表面処理が施された基 材 （ガラス基材等） の表面について接触角計 （例えば、 協和界面科学社製の
Figure imgf000015_0001
（製品名） 等） を用いてドデカンの接触角 （ ¢1 6 9） を測定したとき、 ドデカンの接触角が相対的に大きいことを意味する 。 具体的には、 ドデカンの接触角が 3 5 ° 以上、 好ましくは 4 0 ° 以上、 よ り好ましくは 5 0 ° 以上である。 [0052] Further, the oil repellency means, for example, a contact angle meter (for example, manufactured by Kyowa Interface Science Co., Ltd.) on the surface of a substrate (glass substrate etc.) which has been surface-treated with the above-mentioned surface treatment agent.
Figure imgf000015_0001
When the contact angle (¢169) of dodecane is measured using (product name) etc., it means that the contact angle of dodecane is relatively large. Specifically, the contact angle of dodecane is 35° or more, preferably 40° or more, more preferably 50° or more.
[0053] 本実施形態に係る表面処理剤によれば、 ガラス、 プラスチック、 繊維、 建 築部材等の被処理基材の表面処理に用いることで、 当該被処理基材の表面に 防汚膜等の機能性薄膜 （表面処理層） を形成することができる。 すなわち、 本実施形態に係る親水性及び撥油性を付与可能な表面処理剤は、 防汚層形成 用表面処理剤として利用することができる。 [0053] According to the surface treatment agent of the present embodiment, when used for the surface treatment of a substrate to be treated such as glass, plastics, fibers, and building members, an antifouling film or the like is formed on the surface of the substrate to be treated. The functional thin film (surface treatment layer) of can be formed. That is, the surface treatment agent according to this embodiment capable of imparting hydrophilicity and oil repellency can be used as a surface treatment agent for forming an antifouling layer.
[0054] [表面処理剤の製造方法] [0054] [Method for producing surface treatment agent]
本実施形態に係る表面処理剤は、 例えば、 上記フッ素含有化合物と、 上記 共重合体とを、 溶媒中、 無触媒条件下で混合させることにより製造され得る The surface treatment agent according to the present embodiment can be produced, for example, by mixing the fluorine-containing compound and the copolymer in a solvent under non-catalyst conditions.
[0055] 上記フッ素含有化合物と上記共重合体との混合比は、 例えば、 上記フッ素 含有化合物 1質量部に対し、 1〜 2 5質量部であるのが好ましく、 2〜 2 0 質量部であるのがより好ましく、 5〜 1 5質量部であるのが特に好ましい。 上記フッ素含有化合物と上記共重合体との混合比が上記範囲内にあることで 〇 2020/175121 14 卩（：171? 2020 /005064 [0055] The mixing ratio of the fluorine-containing compound and the copolymer is, for example, preferably 1 to 25 parts by mass, and 2 to 20 parts by mass with respect to 1 part by mass of the fluorine-containing compound. Is more preferable, and 5 to 15 parts by mass is particularly preferable. When the mixing ratio of the fluorine-containing compound and the copolymer is within the above range 〇 2020/175 121 14 卩 (: 171? 2020 /005064
、 得られる表面処理剤において優れた親水性及び撥油性が発現され得る。 上 記共重合体が式 （3） で示される化学構造を有するもの （構成成分として力 ルボン酸を含むもの） である場合、 上記フッ素含有化合物 1質量部に対し、The surface treatment agent obtained can exhibit excellent hydrophilicity and oil repellency. When the above-mentioned copolymer has the chemical structure represented by the formula (3) (containing carboxylic acid as a constituent), 1 part by mass of the above-mentioned fluorine-containing compound:
1質量部以上であるのが好ましく、 5〜 1 5質量部であるのが特に好ましい 。 当該混合比が上記範囲外であると、 所望とする親水性が発現され難くなる おそれがある。 It is preferably 1 part by mass or more, and particularly preferably 5 to 15 parts by mass. If the mixing ratio is out of the above range, desired hydrophilicity may not be easily exhibited.
[0056] 上記溶媒は、 上記フッ素含有化合物と上記共重合体との反応生成物をミセ ル状態で存在させ得るものであればよく、 例えば、 炭素数 1〜 5のアルコー ル系溶媒 （メタノール、 エタノール、 プロパノール、 ブタノール等） であれ ばよく、 炭素数 4以上のアルコール系溶媒が用いられる場合には、 ノルマル アルコールであるのが好ましい。 かかるアルコール系溶媒は僅かに水を含ん でいてもよいが、 アルコール濃度が 9 5容量％以上であればよく、 9 8容量 %以上であるのが好ましい。 アルコール系溶媒に水が 5容量％を超えて含ま れていると、 上記フッ素含有化合物と上記共重合体との反応生成物をミセル 状態で存在させることが困難となるおそれがある。 [0056] The solvent may be any solvent as long as it allows a reaction product of the fluorine-containing compound and the copolymer to exist in a micellar state. For example, an alcohol solvent having 1 to 5 carbon atoms (methanol, Ethanol, propanol, butanol, etc.), and when an alcohol solvent having 4 or more carbon atoms is used, normal alcohol is preferable. The alcoholic solvent may contain a slight amount of water, but the alcohol concentration may be 95% by volume or more, and preferably 98% by volume or more. If the alcohol-based solvent contains water in an amount of more than 5% by volume, it may be difficult to allow the reaction product of the fluorine-containing compound and the copolymer to exist in a micelle state.
[0057] [表面処理方法] [0057] [Surface treatment method]
本実施形態における表面処理方法は、 本実施形態に係る表面処理剤を被処 理基材の表面に塗布する工程を含む。 表面処理剤を被処理基材の表面に塗布 する方法としては、 特に限定されるものではなく、 例えば、 刷毛、 口ーラー 、 スプレー等を用いて塗布する方法や、 表面処理剤に被処理基材を浸潰させ る方法等が挙げられる。 The surface treatment method according to the present embodiment includes a step of applying the surface treatment agent according to the present embodiment onto the surface of a substrate to be treated. The method of applying the surface treatment agent to the surface of the substrate to be treated is not particularly limited, and examples thereof include a method of applying using a brush, a mouth roller, a spray, or the like. And the like.
[0058] 本実施形態において、 表面処理剤を被処理基材の表面に塗布することで形 成された塗膜を加熱することで、 溶媒を除去してもよい。 加熱方法としては 、 オーブンによる加熱、 熱プレスによる加熱等が挙げられるが、 特に制限さ れるものではない。 加熱条件としては、 例えば、 1 0 0〜 1 8 0 °〇で 1 〇〜 6 0分程度、 好ましくは 1 0 0〜 1 3 0 °〇で 1 〇〜 3 0分程度である。 In the present embodiment, the solvent may be removed by heating the coating film formed by applying the surface treatment agent to the surface of the substrate to be treated. Examples of the heating method include heating with an oven and heating with a hot press, but are not particularly limited. The heating conditions are, for example, 100 to 180 ° 〇 and 10 to 60 minutes, preferably 100 to 130 ° 〇 and 10 to 30 minutes.
[0059] 上述したように、 本実施形態に係る表面処理剤を用いた表面処理方法を実 施することで、 被処理基材の表面 （被処理面） に表面処理層が形成されてな 〇 2020/175121 15 卩（：171? 2020 /005064 As described above, by performing the surface treatment method using the surface treatment agent according to the present embodiment, a surface treatment layer is not formed on the surface (treatment surface) of the substrate to be treated. 〇 2020/175 121 15 卩(: 171-1? 2020/005064
る表面処理基材を作製することができる。 かかる表面処理基材において、 表 面処理層は、 基部としての被処理基材の表面 （第 1面） に少なくとも形成さ れていればよいが、 裏面 （第 2面） に形成されていてもよい。 このようにし て作製された表面処理基材においては、 その表面処理層が優れた親水性及び 撥油性を発現することができる。 It is possible to prepare a surface-treated base material. In such a surface-treated base material, the surface-treated layer may be formed at least on the surface (first surface) of the base material to be treated, but may be formed on the back surface (second surface). Good. In the surface-treated substrate thus produced, the surface-treated layer can exhibit excellent hydrophilicity and oil repellency.
[0060] 以上説明した実施形態は、 本発明の理解を容易にするために記載されたも のであって、 本発明を限定するために記載されたものではない。 したがって 、 上記実施形態に開示された各要素は、 本発明の技術的範囲に属するすべて の設計変更や均等物をも含む趣旨である。 The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above-described embodiment is intended to include all design changes and equivalents within the technical scope of the present invention.
実施例 Example
[0061] 以下、 試験例等を挙げて本発明をさらに詳細に説明するが、 本発明は下記 の試験例等に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Test Examples and the like, but the present invention is not limited to the following Test Examples and the like.
[0062] [試料 1 ] [0062] [Sample 1]
上記式 （5） で示されるフッ素含有化合物 20 9と、 上記式 （2_ 1） で示されるジアリルジメチルアンモニウムクロリ ド · アクリルアミ ド共重合 体 （ 3_」 _4 1 , ニッ トーボーメディカル社製， 重量平均分子量： 1 0000） 1 00
Figure imgf000017_0001
とを、 溶媒としてのメタノールに添加し、 室温で 3時 間攪拌することで、 表面処理剤を調製した。 A fluorine-containing compound 20 9 represented by the above formula (5), the formula (2_ 1) diallyldimethylammonium represented by black Li de acrylamide copolymer (3_ "- 4 1, Stevenage toe bow Medical Co., weight Average molecular weight: 1 0000) 100
Figure imgf000017_0001
And were added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.
[0063] [試料 2] [0063] [Sample 2]
ジアリルジメチルアンモニウムクロリ ド · アクリルアミ ド共重合体の添加 量を 300 9に変更した以外は、 試料 1 と同様にして表面処理剤を調製し た。 A surface treatment agent was prepared in the same manner as in Sample 1, except that the addition amount of the diallyldimethylammonium chloride·acrylic amide copolymer was changed to 3009.
[0064] [試料 3] [0064] [Sample 3]
上記式 （5） で示されるフッ素含有化合物 20 9と、 上記式 （2_ 1） で示されるジアリルジメチルアンモニウムクロリ ド · アクリルアミ ド共重合 体 （ 3_」 _81 , ニッ トーボーメディカル社製， 重量平均分子量： 1 80000） 1 0
Figure imgf000017_0002
とを、 溶媒としてのメタノールに添加し、 室温で 3 時間攪拌することで、 表面処理剤を調製した。 〇 2020/175121 16 卩（：171? 2020 /005064 A fluorine-containing compound 20 9 represented by the above formula (5), the formula (2_ 1) diallyldimethylammonium represented by black Li de acrylamide copolymer (3_ "_81, Stevenage toe bow Medical Co., weight average Molecular weight: 1 80 000) 10
Figure imgf000017_0002
And were added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent. 〇 2020/175 121 16 卩 (: 171-1? 2020 /005064
[0065] [試料 4] [0065] [Sample 4]
ジアリルジメチルアンモニウムクロリ ド · アクリルアミ ド共重合体の添加 量を 300 9に変更した以外は、 試料 3と同様にして表面処理剤を調製し た。 A surface treatment agent was prepared in the same manner as in Sample 3, except that the addition amount of the diallyldimethylammonium chloride·acrylic amide copolymer was changed to 3009.
[0066] [試料 5] [0066] [Sample 5]
上記式 （5） で示されるフッ素含有化合物 20 9と、 上記式 （2_ 1） で示されるジアリルジメチルアンモニウムクロリ ド · アクリルアミ ド共重合 体 （ 3_」 _81
Figure imgf000018_0001
ニッ トーボーメディカル社製， 重量平均分子量：A fluorine-containing compound 20 9 represented by the above formula (5), the formula (2_ 1) diallyldimethylammonium represented by black Li de acrylamide copolymer (3_ "_81
Figure imgf000018_0001
Nittobo Medical, weight average molecular weight:
1 0000） 1 0
Figure imgf000018_0002
とを、 溶媒としてのメタノールに添加し、 室温で 3 時間攪拌することで、 表面処理剤を調製した。 1 0000) 1 0
Figure imgf000018_0002
And were added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.
[0067] [試料 6] [0067] [Sample 6]
ジアリルジメチルアンモニウムクロリ ド · アクリルアミ ド共重合体の添加 量を 300 9に変更した以外は、 試料 5と同様にして表面処理剤を調製し た。 A surface treatment agent was prepared in the same manner as in Sample 5, except that the addition amount of the diallyldimethylammonium chloride·acrylic amide copolymer was changed to 3009.
[0068] [試料 7] [0068] [Sample 7]
上記式 （5） で示されるフッ素含有化合物 20〇! 9と、 上記式 （3_ 1） で示されるジアリルエチルメチルアンモニウムエチルサルフェイ ト ·マレイ ン酸共重合体 （ 八3_245 1 , ニッ トーボーメディカル社製， 重量平均 分子量 = 30000） 1 0
Figure imgf000018_0003
とを、 溶媒としてのメタノールに添加し、 室温で 3時間攪拌することで、 表面処理剤を調製した。 Fluorine-containing compound 200○!9 represented by the above formula (5) and diallylethylmethylammoniumethylsulfate-maleic acid copolymer represented by the above formula (3_1) (8 3_245 1, Nittobo Medical Manufactured by the company, weight average molecular weight = 30000) 10
Figure imgf000018_0003
And were added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.
[0069] [試料 8] [0069] [Sample 8]
ジアリルエチルメチルアンモニウムエチルサルフェイ ト ·マレイン酸共重 合体の添加量を 300 9に変更した以外は、 試料 7と同様にして表面処理 剤を調製した。 A surface treatment agent was prepared in the same manner as in Sample 7, except that the addition amount of the diallylethylmethylammoniumethylsulfate·maleic acid copolymer was changed to 3009.
[0070] [試料 9] [0070] [Sample 9]
上記式 （5） で示されるフッ素含有化合物 20 9と、 上記式 （3_2） で示されるジアリルジメチルアンモニウムクロリ ド ·マレイン酸共重合体 （ 八3— 235 1 , ニッ トーボーメディカル社製， 重量平均分子量 = 250 〇 2020/175121 17 卩（：171? 2020 /005064 A fluorine-containing compound 20 9 represented by the above formula (5), diallyldimethylammonium Li de maleic acid copolymer represented by the above formula (3_2) (eight 3-235 1, Stevenage toe bow Medical Co., weight average Molecular weight = 250 〇 2020/175 121 17 卩(: 171-1? 2020/005064
〇〇） 1
Figure imgf000019_0001
とを、 溶媒としてのメタノールに添加し、 室温で 3時間攪 拌することで、 表面処理剤を調製した。 〇 〇) 1
Figure imgf000019_0001
And were added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.
[0071] [試料 1 0] [0071] [Sample 10]
ジアリルジメチルアンモニウムクロリ ド ·マレイン酸共重合体の添加量を 300 9に変更した以外は、 試料 9と同様にして表面処理剤を調製した。 A surface treating agent was prepared in the same manner as in Sample 9 except that the addition amount of the diallyldimethylammonium chloride/maleic acid copolymer was changed to 3009.
[0072] [試料 1 1 ] [0072] [Sample 1 1]
上記式 （5） で示されるフッ素含有化合物 2〇 9と、 下記式 （1 0） で 示される 3 -クロロー 2 -ヒドロキシプロピル化ジアリルアミン塩酸塩 ·ジ アリルジメチルアンモニウムクロリ ド共重合体 （ 八3-880, ニッ トー ボーメディカル社製， 重量平均分子量 = 40000） 1 00 9とを、 溶媒 としてのメタノールに添加し、 室温で 3時間攪拌することで、 表面処理剤を 調製した。 A fluorine-containing compound 209 represented by the above formula (5) and 3-chloro-2-hydroxypropylated diallylamine hydrochloride represented by the following formula (10)·diallyldimethylammonium chloride copolymer (8 3- 880, manufactured by Nittobo Medical, Inc., weight average molecular weight = 40,000) 1009 was added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.
[0073] [化 20] [0073] [Chemical 20]
Figure imgf000019_0002
Figure imgf000019_0002
[0074] [試料 1 2] [0074] [Sample 1 2]
3 -クロロー 2 -ヒドロキシプロピル化ジアリルアミン塩酸塩 ·ジアリル ジメチルアンモニウムクロリ ド共重合体の添加量を 3
Figure imgf000019_0003
9に変更した以 外は、 試料 1 1 と同様にして表面処理剤を調製した。 3-Chloro-2-hydroxypropylated diallylamine hydrochloride·The amount of diallyldimethylammonium chloride copolymer added was 3
Figure imgf000019_0003
A surface treatment agent was prepared in the same manner as in Sample 11 except that the surface treatment agent was changed to 9.
[0075] [試料 1 3] [0075] [Sample 1 3]
上記式 （5） で示されるフッ素含有化合物 2〇 9と、 下記式 （1 1） で 示されるジアリルアミン塩酸塩 · アクリルアミ ド共重合体 （ 八3-2 1 4 1 〇1_, ニッ トーボーメディカル社製， 重量平均分子量： 1 0000） 1 0 〇 2020/175121 18 卩（：171? 2020 /005064 Fluorine-containing compound 209 represented by the above formula (5) and diallylamine hydrochloride/acrylic amide copolymer represented by the following formula (1 1) (8 3-2 1 4 1 〇 1_, Nittobo Medical Company, weight average molecular weight: 10000) 10 〇 2020/175 121 18 卩(: 171-1? 2020/005064
〇 9とを、 溶媒としてのメタノールに添加し、 室温で 3時間攪拌すること で、 表面処理剤を調製した。 O and 9 were added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.
[0076] [化 21] [0076] [Chemical 21]
Figure imgf000020_0001
Figure imgf000020_0001
[0077] [試料 1 4] [0077] [Sample 1 4]
ジアリルアミン塩酸塩 · アクリルアミ ド共重合体の添加量を 300
Figure imgf000020_0002
9に 変更した以外は、 試料 1 1 と同様にして表面処理剤を調製した。 Diallylamine Hydrochloride · Addition amount of acrylic amide copolymer is 300
Figure imgf000020_0002
A surface treatment agent was prepared in the same manner as Sample 11 except that the surface treatment agent was changed to 9.
[0078] [試料 1 5] [0078] [Sample 15]
塩基性触媒としてのアンモニア水
Figure imgf000020_0003
試料 3 と同様にして表面処理剤を調製した。 Ammonia water as basic catalyst
Figure imgf000020_0003
A surface treatment agent was prepared in the same manner as in Sample 3.
[0079] [試料 1 6] [0079] [Sample 1 6]
塩基性触媒としてのアンモニア水
Figure imgf000020_0004
試料 4 と同様にして表面処理剤を調製した。 Ammonia water as basic catalyst
Figure imgf000020_0004
A surface treatment agent was prepared in the same manner as in Sample 4.
[0080] [試料 1 7 ] [0080] [Sample 17]
塩基性触媒としてのアンモニア水
Figure imgf000020_0005
試料 7 と同様にして表面処理剤を調製した。 Ammonia water as basic catalyst
Figure imgf000020_0005
A surface treatment agent was prepared in the same manner as in Sample 7.
[0081] [試料 1 8] [0081] [Sample 18]
塩基性触媒としてのアンモニア水
Figure imgf000020_0006
試料 8 と同様にして表面処理剤を調製した。 Ammonia water as basic catalyst
Figure imgf000020_0006
A surface treatment agent was prepared in the same manner as in Sample 8.
[0082] 〔試験例 1〕 接触角測定試験 [Test Example 1] Contact angle measurement test
第 1面及びそれに対向する第 2面を有し、 第 1面に対して塩素系溶剤 （1 , 2—ジクロロエタン） を用いた脱脂処理が施されたガラス （被処理基材） を準備し、 当該ガラスの第 1面に対しスピンコート法 （回転数： 2000 「 ， 回転時間： 303, 滴下量： 0. 3mL） により表面処理剤 （試料 1 〇 2020/175121 19 卩（：171? 2020 /005064 Prepare a glass (substrate to be processed) that has a first surface and a second surface opposite to it, and has been degreased with a chlorine-based solvent (1,2-dichloroethane) on the first surface, The surface treatment agent (Sample 1) was applied to the first surface of the glass by spin coating (rotation speed: 2000 ", rotation time: 303, drop amount: 0.3 mL). 〇 2020/175 121 19 卩(: 171-1? 2020/005064
〜 1 8） の塗膜を形成することで、 表面処理基材を得た。 当該表面処理基材 における水及びドデカンの接触角 （ 6 9） を、 接触角計 （協和界面科学社 製， 製品名
Figure imgf000021_0001
を用いて測定した。 結果を表 1 に示す。 表 1 において水接触角 （0〇! 丨 n） 及びドデカン接触角は、 それぞ れ、 表面処理基材に水及びドデカンを滴下直後の接触角測定結果であり、 水 接触角 （3 0 丨 n） は、 表面処理基材に水を滴下してから 3 0分経過後の 接触角測定結果である。 なお、 参考として、 表面処理剤による表面処理を行 う前のガラス （試料 1 9） における水及びドデカンの接触角 （〇1 6 9） の測 定結果もあわせて表 1 に す。 ~ 18) to form a coating film to obtain a surface-treated substrate. The contact angle (69) of water and dodecane on the surface-treated substrate was measured using a contact angle meter (Kyowa Interface Science Co., Ltd., product name
Figure imgf000021_0001
Was measured using. The results are shown in Table 1. In Table 1, the water contact angle (0 〇! 丨 n) and the dodecane contact angle are the contact angle measurement results immediately after dripping water and dodecane on the surface-treated substrate, respectively, and the water contact angle (30 丨n) ) Is the contact angle measurement result 30 minutes after water was dropped on the surface-treated substrate. Note that reference, the contact angle of water and dodecane in row Cormorants front glass surface treatment (Sample 1 9) by surface treatment agent (Rei_1 6 9) of the measurement results together to in Table 1.
[0083] [表 1 ] [0083] [Table 1]
Figure imgf000021_0002
Figure imgf000021_0002
[0084] 上記表 1 に示すように、 所定のフッ素含有化合物と、 アリルアミンの 4級 アンモニウム塩及びアミ ド化合物の共重合体 （上記式 （2 _ 1） で示される ジアリルジメチルアンモニウムクロリ ド · アクリルアミ ド共重合体） との反 応生成物を含む表面処理剤は、 優れた親水性及び撥油性を付与可能であるこ 〇 2020/175121 20 卩（：171? 2020 /005064 [0084] As shown in Table 1 above, a copolymer of a predetermined fluorine-containing compound, a quaternary ammonium salt of allylamine and an amide compound (diallyldimethylammonium chloride-acrylic represented by the above formula (2 _ 1) A surface treatment agent containing a reaction product with an amide copolymer can impart excellent hydrophilicity and oil repellency. 〇 2020/175 121 20 boxes (: 171-1? 2020 /005064
とが確認された。 また、 所定のフッ素含有化合物と、 アリルアミンの 4級ア ンモニウム塩及びカルボン酸の共重合体 （上記式 （3 - 1） で示されるジア リルエチルメチルアンモニウムエチルサルフェイ ト · マレイン酸共重合体、 上記式 （3— 2） で示されるジアリルジメチルアンモニウムクロリ ド · マレ イン酸共重合体） との反応生成物を含む表面処理剤は、 優れた親水性及び撥 油性を付与することができることが確認された。 なお、 試料 1 9 （未処理ガ ラス） における水の接触角 （3 0 丨 n） が接触角 （〇 丨 n） よりも小さ くなっているのは、 揮発により水滴が小さくなったことによるものであった Was confirmed. Further, a predetermined fluorine-containing compound, a copolymer of a quaternary ammonium salt of allylamine and a carboxylic acid (a diarylethylmethylammonium ethylsulfate-maleic acid copolymer represented by the above formula (3-1)), It was confirmed that the surface treatment agent containing the reaction product with the diallyldimethylammonium chloride·maleic acid copolymer represented by the above formula (3-2) can impart excellent hydrophilicity and oil repellency. Was done. The water contact angle (30 丨 n) of sample 19 (untreated glass) was smaller than the contact angle (〇 丨 n) because water droplets became smaller due to volatilization. Met
[0085] 一方で、 構成成分の一つがアミ ド化合物ではない上記式 （ 1 0） で示され る 3 -クロロー 2 -ヒドロキシプロピル化ジアリルアミン塩酸塩 ·ジアリル ジメチルアンモニウムクロリ ド共重合体を含む表面処理剤 （試料 1 1 , 1 2 ） は、 撥油性を付与可能であるものの、 親水性を付与することができないこ とが確認された。 また、 構成成分の一つがアリルアミンの 4級アンモニウム 塩ではない上記式 （1 1） で示されるジアリルアミン塩酸塩 · アクリルアミ ド共重合体を含む表面処理剤 （試料 1 3 , 1 4） においても同様に、 撥油性 を付与可能であるものの、 親水性を付与することができないことが確認され た。 これらの結果から、 所定のフッ素化合物との反応生成物とを形成する共 重合体の構成成分が、 アリルアミンの 4級アンモニウム塩とアミ ド化合物又 はカルボン酸とであることで、 当該反応生成物を含む表面処理剤において優 れた親水性及び撥油性を付与可能であることが明らかとなった。 [0085] On the other hand, a surface treatment containing 3-chloro-2-hydroxypropylated diallylamine hydrochloride-diallyldimethylammonium chloride copolymer represented by the above formula (10) in which one of the constituent components is not an amide compound It was confirmed that the agents (Samples 1 1 and 12) were able to impart oil repellency, but not hydrophilicity. The same applies to the surface-treating agent (Samples 1 3 and 1 4) containing the diallylamine hydrochloride·acrylic amide copolymer represented by the above formula (1 1) in which one of the constituents is not the quaternary ammonium salt of allylamine It was confirmed that, although oil repellency can be imparted, hydrophilicity cannot be imparted. From these results, it is confirmed that the constituents of the copolymer that forms the reaction product with the predetermined fluorine compound are the quaternary ammonium salt of allylamine and the amide compound or the carboxylic acid. It has been clarified that excellent hydrophilicity and oil repellency can be imparted to the surface treatment agent containing
[0086] また、 各表面処理剤 （試料 1〜 1 8） を目視した結果、 触媒を含まない反 応系で生成された反応生成物を含む表面処理剤 （試料 1〜 1 4） はいずれも 無色透明であるのに対し、 塩基性触媒 （アンモニア水） を含む反応系で生成 される反応生成物を含む表面処理剤 （試料 1 5〜 1 8） は顕著に白濁してい ることが確認された。 さらに、 試料 1〜 1 4の表面処理剤で表面処理が施さ れたガラス （被処理基材） の表面においては、 無色透明であり、 視認性が確 保されているのに対し、 試料 1 5〜 1 8の表面処理剤で表面処理が施された 〇 2020/175121 21 卩（：171? 2020 /005064 [0086] Further, as a result of visually observing each surface treatment agent (Samples 1 to 18), it was found that all the surface treatment agents (Samples 1 to 14) containing the reaction product generated in the reaction system containing no catalyst were found. Although it is colorless and transparent, it was confirmed that the surface treatment agent (Samples 15 to 18) containing the reaction product produced in the reaction system containing the basic catalyst (ammonia water) was remarkably clouded. It was Furthermore, the surface of the glass (substrate to be treated) that has been surface-treated with the surface-treating agent of Samples 1 to 14 is colorless and transparent, and its visibility is assured. Surface treated with ~18 surface treatment agents 〇 2020/175 121 21 卩 (: 171-1? 2020 /005064
ガラス （被処理基材） の表面においては、 わずかに白濁しており、 視認性が 不十分であることが確認された。 この結果から、 無触媒条件下で得られる反 応生成物を含む表面処理剤であれば、 無色透明の表面処理層を被処理基材上 に形成可能であり、 表面処理層を有する表面処理基材の視認性を確保可能で あることが明らかとなった。 It was confirmed that the surface of the glass (substrate to be treated) was slightly clouded, and the visibility was insufficient. From this result, it is possible to form a colorless and transparent surface treatment layer on the substrate to be treated with the surface treatment agent containing the reaction product obtained under the non-catalyst condition, and to obtain the surface treatment group having the surface treatment layer. It became clear that the visibility of the material can be secured.
産業上の利用可能性 Industrial availability
[0087] 本発明は、 親水性と撥油性とが要求される製品の技術分野において有用で ある。 The present invention is useful in the technical field of products requiring hydrophilicity and oil repellency.

Claims

〇 2020/175121 22 卩（：171? 2020 /005064 請求の範囲 〇 2020/175 121 22 卩(: 171-1? 2020/005064 Claims
[請求項 1 ] 下記式 （1） で示されるフッ素含有化合物と、 アリルアミンの 4級 アンモニウム塩及びアミ ド化合物又はカルボン酸の共重合体と、 溶媒 とを含有することを特徴とする表面処理剤。 [Claim 1] A surface treatment agent comprising a fluorine-containing compound represented by the following formula (1), a quaternary ammonium salt of allylamine and a copolymer of an amide compound or a carboxylic acid, and a solvent. ..
[化 1 ]
Figure imgf000024_0001
[Chemical 1]
Figure imgf000024_0001
上記式 （1） 中、 はフルオロアルキル基を含有する基を表し、 In the above formula (1), represents a group containing a fluoroalkyl group,
Vはアルキル基又はアルコキシアルキル基を表し、 V及び は各々 独立して水素原子又は 1価の有機基を表し、 Xは 1〜 1 0 0の整数で あり、 ソは〇〜 1 0 0の整数である。 V represents an alkyl group or an alkoxyalkyl group, V and each independently represent a hydrogen atom or a monovalent organic group, X is an integer of 1 to 100, and so is an integer of 0 to 100. Is.
[請求項 2] 前記共重合体が、 下記式 （2） で示される化学構造を有することを 特徴とする請求項 1 に記載の表面処理剤。 [Claim 2] The surface treating agent according to claim 1, wherein the copolymer has a chemical structure represented by the following formula (2).
[化 2] [Chemical 2]
Figure imgf000024_0002
Figure imgf000024_0002
上記式 （2） 中、 ’ 及· 0^’ は各々独立して炭素数 1〜 4のア ルキル基を表し、 Xはハロゲン化物イオン、 無機アニオン又は有機ア ニオンを表す。 In the above formula (2),' and 0^' each independently represent an alkyl group having 1 to 4 carbon atoms, and X represents a halide ion, an inorganic anion or an organic anion.
[請求項 3] 前記共重合体が、 下記式 （3） で示される化学構造を有することを 特徴とする請求項 1 に記載の表面処理剤。 \¥02020/175121 23 卩（：171?2020/005064 [Claim 3] The surface treatment agent according to claim 1, wherein the copolymer has a chemical structure represented by the following formula (3). \¥02020/175121 23 ((171?2020/005064
Figure imgf000025_0001
Figure imgf000025_0001
上記式 （3） 中、
Figure imgf000025_0002
及び［¾ は各々独立して炭素数 1〜 4のア ルキル基を表し、 Xはハロゲン化物イオン、 無機アニオン又は有機ア ニオンを表す。 In the above formula (3),
Figure imgf000025_0002
And [¾ each independently represent an alkyl group having 1 to 4 carbon atoms, and X represents a halide ion, an inorganic anion or an organic anion.
［請求項 4］ 前記フッ素含有化合物と前記共重合体との含有比 （質量基準） が、 [Claim 4] The content ratio (mass basis) of the fluorine-containing compound and the copolymer is
1 : 1〜 2 5であることを特徴とする請求項 1〜 3のいずれかに記載 の表面処理剤。 The surface treatment agent according to any one of claims 1 to 3, wherein the surface treatment agent is 1:1 to 25.
［請求項 5］ 前記溶媒が、 炭素数 1〜 5のアルコール系溶媒であることを特徴と する請求項 1〜 4のいずれかに記載の表面処理剤。 [Claim 5] The surface treatment agent according to any one of claims 1 to 4, wherein the solvent is an alcohol solvent having 1 to 5 carbon atoms.
［請求項 6］ 前記アリルアミンの 4級アンモニウム塩及びアミ ド化合物の共重合 体の重量平均分子量が、 1 5 0 0 0 0以上であることを特徴とする請 求項 1〜 5のいずれかに記載の表面処理剤。 [Claim 6] The weight average molecular weight of the copolymer of a quaternary ammonium salt of allylamine and an amide compound is 150 000 or more, and any one of claims 1 to 5 is characterized in that The surface treatment agent described.
［請求項 7］ 前記式 （1） において、 Vが 0であることを特徴とする請求項 1〜 [Claim 7] In the formula (1), V is 0.
6のいずれかに記載の表面処理剤。 The surface treatment agent according to any one of 6.
［請求項 8］ 前記式 （1） において、 で表されるフルオロアルキル基を含有 する基が、 下記式 （4） で表される基であることを特徴とする請求項 1〜 7のいずれかに記載の表面処理剤。 [Claim 8] In the above formula (1), the group containing a fluoroalkyl group represented by: is a group represented by the following formula (4): The surface treatment agent according to.
［化 4］ [Chemical 4]
-〇ド 3）［0〇 2。 ）］（）0〇^7 （4） -〇 de 3) [0_Rei 2. )] () 0 ^ 7 (4)
上記式 （4） 中、 は〇〜 2の整数である。 In the above formula (4), is an integer from 0 to 2.
［請求項 9］ 前記式 （1） において、 はメチル基であることを特徴とする請 求項 1〜 8のいずれかに記載の表面処理剤。 〇 2020/175121 24 卩（：171? 2020 /005064 [Claim 9] The surface treating agent according to any one of claims 1 to 8, wherein in the formula (1), is a methyl group. 〇 2020/175 121 24 卩 (: 171-1? 2020 /005064
[請求項 10] 前記式 （1） において、 Xが 1〜 1 0の整数であることを特徴とす る請求項 1〜 9のいずれかに記載の表面処理剤。 10. The surface treatment agent according to claim 1, wherein in the formula (1), X is an integer of 1 to 10.
[請求項 1 1 ] 第 1面及び当該第 1面に対向する第 2面を有する基部と、 [Claim 11] A base having a first surface and a second surface facing the first surface,
前記基部の少なくとも前記第 1面に設けられてなる表面処理層と を備え、 A surface treatment layer formed on at least the first surface of the base,
前記表面処理層は、 請求項 1〜 1 0のいずれかに記載の表面処理剤 を用いた表面処理が前記基部の前記第 1面に施されることにより形成 されてなるものであることを特徴とする表面処理基材。 The surface treatment layer is formed by applying a surface treatment using the surface treatment agent according to any one of claims 1 to 10 to the first surface of the base portion. And a surface-treated substrate.
[請求項 12] 下記式 （1） で示されるフッ素含有化合物と、 アリルアミンの 4級 アンモニウム塩及びアミ ド化合物又はカルボン酸の共重合体と、 溶媒 とを混合することを特徴とする表面処理剤の製造方法。 [Claim 12] A surface treatment agent comprising a fluorine-containing compound represented by the following formula (1), a quaternary ammonium salt of allylamine and a copolymer of an amide compound or a carboxylic acid, and a solvent. Manufacturing method.
[化 5]
Figure imgf000026_0001
[Chemical 5]
Figure imgf000026_0001
上記式 （1） 中、 はフルオロアルキル基を含有する基を表し、 In the above formula (1), represents a group containing a fluoroalkyl group,
Vはアルキル基又はアルコキシアルキル基を表し、 V及び は各々 独立して水素原子又は 1価の有機基を表し、 Xは 1〜 1 0 0の整数で あり、 ソは〇〜 1 0 0の整数である。 V represents an alkyl group or an alkoxyalkyl group, V and each independently represent a hydrogen atom or a monovalent organic group, X is an integer of 1 to 100, and so is an integer of 0 to 100. Is.
[請求項 13] 酸触媒及びアルカリ触媒のいずれをも混合させないことを特徴とす る請求項 1 2に記載の表面処理剤の製造方法。 [Claim 13] The method for producing a surface treatment agent according to claim 12, wherein neither an acid catalyst nor an alkali catalyst is mixed.
[請求項 14] 請求項 1〜 1 〇のいずれかに記載の表面処理剤を用いて被処理基材 に表面処理を施すことを特徴とする表面処理方法。 [Claim 14] A surface treatment method comprising subjecting a substrate to be treated to a surface treatment using the surface treatment agent according to any one of claims 1 to 10.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008297482A (en) * 2007-06-01 2008-12-11 Agc Seimi Chemical Co Ltd Resin composition, resin-molded product and coating using the same
WO2012008269A1 (en) * 2010-07-15 2012-01-19 日東紡績株式会社 Anti-corrosive agent for washing of metal with acid, detergent solution composition, and method for washing of metal
JP2015187220A (en) * 2014-03-26 2015-10-29 国立大学法人弘前大学 Fluorine-containing nanocomposite particle and method of producing the same, and coating agent, oil water separation film, and resin composition comprising the same
WO2017034616A1 (en) * 2015-08-24 2017-03-02 Ohio State Innovation Foundation Multilayer coatings and methods of making and using thereof
JP2018141089A (en) * 2017-02-28 2018-09-13 藤倉ゴム工業株式会社 Water-resistant composition, water-resistant film, and method for producing the same
JP2018141063A (en) * 2017-02-28 2018-09-13 藤倉ゴム工業株式会社 Surface treatment agent and method for producing the same, filter, and surface treatment method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6664787B2 (en) * 2016-02-24 2020-03-13 藤倉コンポジット株式会社 Nanocomposite particles, column packing material, surface treatment agent, filter, method for producing nanocomposite particle dispersion and surface treatment method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008297482A (en) * 2007-06-01 2008-12-11 Agc Seimi Chemical Co Ltd Resin composition, resin-molded product and coating using the same
WO2012008269A1 (en) * 2010-07-15 2012-01-19 日東紡績株式会社 Anti-corrosive agent for washing of metal with acid, detergent solution composition, and method for washing of metal
JP2015187220A (en) * 2014-03-26 2015-10-29 国立大学法人弘前大学 Fluorine-containing nanocomposite particle and method of producing the same, and coating agent, oil water separation film, and resin composition comprising the same
WO2017034616A1 (en) * 2015-08-24 2017-03-02 Ohio State Innovation Foundation Multilayer coatings and methods of making and using thereof
JP2018141089A (en) * 2017-02-28 2018-09-13 藤倉ゴム工業株式会社 Water-resistant composition, water-resistant film, and method for producing the same
JP2018141063A (en) * 2017-02-28 2018-09-13 藤倉ゴム工業株式会社 Surface treatment agent and method for producing the same, filter, and surface treatment method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOÃO B. P. SOARES, FERNANDA L. MOTTA: "Using polymer reaction engineering principles to help the environment: the case of the Canadian oil sands tailings", JOURNAL OF THE BRAZILIAN CHEMICAL SOCIETY, vol. 30, no. 3, 3 October 2018 (2018-10-03), pages 426 - 435, XP055734908, ISSN: 0103-5053, DOI: 10.21577/0103-5053.20180197 *

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