WO2019235143A1 - Agent oléophobe hydrophile - Google Patents

Agent oléophobe hydrophile Download PDF

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Publication number
WO2019235143A1
WO2019235143A1 PCT/JP2019/018981 JP2019018981W WO2019235143A1 WO 2019235143 A1 WO2019235143 A1 WO 2019235143A1 JP 2019018981 W JP2019018981 W JP 2019018981W WO 2019235143 A1 WO2019235143 A1 WO 2019235143A1
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meth
acrylate
mass
group
oil repellent
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PCT/JP2019/018981
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English (en)
Japanese (ja)
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徹 岩木
元城 池田
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第一工業製薬株式会社
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Publication of WO2019235143A1 publication Critical patent/WO2019235143A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
    • 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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • 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 hydrophilic oil repellent having excellent hydrophilicity, oil repellency, and oil removability.
  • the fluorine-containing alkyl group has water repellency as well as oil repellency, and water / oil repellents using such properties have been widely used.
  • a hydrophilic oil repellent that can impart both hydrophilicity and oil repellency to the surface of an object allows the oil adhering to the surface to be easily washed away with water alone, but has sufficient performance. The hydrophilic oil repellent which has not been obtained yet.
  • Cited Document 1 discloses such a hydrophilic oil repellent having both hydrophilicity and oil repellency. As can be seen from the description of the examples (for example, paragraph 0110), water is used to remove dirt. It was necessary to wash away sufficiently, and the oil removal property was insufficient.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a hydrophilic oil repellent that is excellent in hydrophilicity, oil repellency, oil removability, durability and wear resistance.
  • the hydrophilic oil repellent of the present invention comprises a constituent monomer containing at least a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a2) having a polyoxyalkylene group. It contains a copolymer obtained by polymerization and a crosslinking agent (b).
  • the component (a2) may be a polyoxyalkylene glycol monoalkyl ether (meth) acrylate.
  • the number of repeating units of the oxyalkylene group in the component (a2) can be 8 or more and 150 or less.
  • the content ratio of the component (a2) may be 100 to 900 parts by mass with respect to 100 parts by mass of the component (a1).
  • (meth) acrylic acid (a3) can be further contained.
  • the copolymer may further contain an alkoxysilyl group-containing (meth) acrylate (a4) as a constituent monomer.
  • the article of the present invention has been treated with the above hydrophilic oil repellent.
  • hydrophilic oil repellent excellent in hydrophilicity, oil repellency, oil removability, durability and abrasion resistance, and an article excellent in antifouling property and dirt removal treated therewithcan be provided.
  • the hydrophilic oil repellent according to the present embodiment contains at least a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a2) having a polyoxyalkylene group. It contains a copolymer obtained by polymerizing constituent monomers and a crosslinking agent (b).
  • “(meth) acrylate” means acrylate or methacrylate.
  • Examples of the (meth) acrylate compound (a1) having a C1-C6 fluoroalkyl group according to the present embodiment include fluoroalkyl (meth) acrylate, fluoroalkylalkylene (meth) acrylate, and fluoroalkylpolyoxyfluoro An alkylene (meth) acrylate etc. are mentioned. Of these, fluoroalkyl (meth) acrylate and fluoroalkylalkylene (meth) acrylate are preferred, and fluoroalkylalkylene (meth) acrylate is more preferred.
  • the fluoroalkyl group is preferably a fluoroalkyl group having 2 to 6 carbon atoms, and more preferably a fluoroalkyl group having 4 to 6 carbon atoms.
  • the fluoroalkyl group is preferably a perfluoroalkyl group.
  • “(per) fluoro” means perfluoro or fluoro.
  • fluoroalkyl (meth) acrylates examples include (per) fluoromethyl (meth) acrylate, (per) fluoroethyl (meth) acrylate, (per) fluoropropyl (meth) acrylate, and (per) fluorobutyl (meth) acrylate. , (Per) fluoropentyl (meth) acrylate, (per) fluorohexyl (meth) acrylate, and the like.
  • fluoroalkyl (meth) acrylate can also be represented by the following general formula (1).
  • Rf-OX (1)
  • Rf is a fluoroalkyl group and X is an acryloyl group or a methacryloyl group.
  • fluoroalkylalkylene (meth) acrylate examples include (per) fluoromethylmethylene (meth) acrylate, (per) fluoromethylethylene (meth) acrylate, (per) fluoroethylmethylene (meth) acrylate, and (per) fluoroethyl.
  • fluoroalkyl alkylene (meth) acrylate can also be represented by the following general formula (2).
  • Rf-YOX (2) Rf is a fluoroalkyl group
  • Y is an alkylene group
  • X is an acryloyl group or a methacryloyl group.
  • fluoroalkyl polyoxyfluoroalkylene (meth) acrylate examples include (per) fluoromethyl polyoxyfluoroethylene (meth) acrylate, (per) fluoroethyl polyoxyfluoroethylene (meth) acrylate, and (per) fluoropropyl polyoxy Fluoroethylene (meth) acrylate, (per) fluorobutyl polyoxyfluoroethylene (meth) acrylate, (per) fluoropentyl polyoxyfluoroethylene (meth) acrylate, (per) fluorohexyl polyoxyfluoroethylene (meth) acrylate, ( Per) fluorohexyl polyoxyfluoropropylene (meth) acrylate and the like.
  • fluoroalkyl polyoxyfluoroalkylene (meth) acrylate can also be represented by the following general formula (3).
  • Rf-Z-OX (3) Rf is a fluoroalkyl group
  • Z is a polyoxyfluoroalkylene group
  • X is an acryloyl group or a methacryloyl group.
  • Examples of the (meth) acrylate compound (a2) having a polyoxyalkylene group according to the present embodiment include those represented by the following general formula (4).
  • the thing applicable to a component (a1) is excluded.
  • R 1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Y is an alkylene group
  • n is an integer of 2 or more
  • X is an acryloyl group or a methacryloyl group.
  • R 1 in the general formula (4) is preferably an alkyl group having 1 to 6 carbon atoms.
  • the compound of the general formula (4) is preferably polyoxyalkylene glycol monoalkyl ether (meth) acrylate, and more preferably polyoxyethylene glycol monomethyl ether methacrylate.
  • the alkylene group in the general formula (4) is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms, since oil removal is more excellent. More preferably, it has 1 to 5 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group. These alkylene groups may have a substituent other than halogen. Among these, an ethylene group and a propylene group are preferable, and an ethylene group is more preferable. Moreover, as a polyoxyalkylene group, one type of these alkylene groups may be polymerized, or two or more types may be polymerized. When two or more types of alkylene groups are polymerized, random polymerization or block polymerization may be used.
  • the number of repeating units n of the oxyalkylene group in the general formula (4) is not particularly limited, but is preferably 8 or more and 150 or less because oil removal and durability are more excellent.
  • the lower limit is more preferably 10 or more, and further preferably 15 or more.
  • the upper limit is more preferably 120 or less, and still more preferably 100 or less.
  • the content ratio of the component (a2) is not particularly limited, it is preferably 100 to 900 parts by mass with respect to 100 parts by mass of the component (a1) because oil removability and durability are more excellent.
  • the lower limit value is more preferably 200 parts by mass or more, and further preferably 300 parts by mass or more.
  • the upper limit value is more preferably 750 parts by mass or less, and further preferably 600 parts by mass or less.
  • the above constituent monomer preferably further includes (a3) (meth) acrylic acid from the viewpoint of improving durability.
  • a3 (meth) acrylic acid examples include acrylic acid and methacrylic acid.
  • the content ratio of the component (a3) is not particularly limited, but is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (a1) because oil removal and durability are more excellent.
  • the lower limit is more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more.
  • the upper limit value is more preferably 30 parts by mass or less.
  • the content ratio of the component (a3) is not particularly limited, but it is 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (a2) because oil removability and durability are more excellent. preferable.
  • the lower limit value is more preferably 1 part by mass or more.
  • the upper limit is more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.
  • the above constituent monomer preferably further includes (a4) an alkoxysilyl group-containing (meth) acrylate from the viewpoint of improving durability.
  • Such compounds include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane. And methoxysilane.
  • the content ratio of the component (a4) is not particularly limited, but is preferably 1 to 60 parts by mass with respect to 100 parts by mass of the component (a1) because durability is more excellent.
  • the lower limit is more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more.
  • the upper limit is more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less.
  • the content ratio of the component (a4) is not particularly limited, but is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (a2) because durability is more excellent.
  • the lower limit value is more preferably 1 part by mass or more.
  • the upper limit value is more preferably 15 parts by mass or less.
  • the constituent monomer may further contain a (meth) acrylate compound (a5) in addition to the components (a1) to (a4) as long as the object of the invention is not adversely affected.
  • a (meth) acrylate compound (a5) examples include alkyl (meth) acrylates, oxyalkylene group-containing (meth) acrylate monomers, and the like.
  • alkyl (meth) acrylate examples include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth).
  • alkyl (meth) acrylate examples include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth).
  • Examples of the oxyalkylene group-containing (meth) acrylate monomer include methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and bisphenol A ethylene oxide. Examples include adduct di (meth) acrylate.
  • glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid amide, N-methylol (meth) acrylic acid Amides, diacetone (meth) acrylic acid amide, isocyanate ethyl (meth) acrylate, (meth) acrylate having polysiloxane, 2-methacryloylethyl acid phosphate, dimethylaminomethyl (meth) acrylate, and the like can also be used.
  • the content of the component (a1) in the constituent monomer is not particularly limited, but is preferably 5 to 50% by mass because oil removal and durability are more excellent.
  • the lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.
  • the upper limit value is more preferably 40% by mass or less, and further preferably 30% by mass or less.
  • the content of the component (a2) in the constituent monomer is not particularly limited, but is preferably 40 to 95% by mass because oil removal and durability are more excellent.
  • the lower limit is more preferably 50% by mass or more, and further preferably 60% by mass or more.
  • the upper limit value is more preferably 94.9% by mass or less, further preferably 94.5% by mass or less, particularly preferably 90% by mass or less, and 85% by mass or less. More preferably, it is more preferably 80% by mass or less.
  • the content of the component (a3) in the constituent monomer is not particularly limited, but is preferably 0.1 to 20% by mass because durability is more excellent.
  • the lower limit is more preferably 0.5% by mass or more, further preferably 0.7% by mass or more, and particularly preferably 0.9% by mass or more.
  • the upper limit value is more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 8% by mass or less.
  • the content of the component (a4) in the constituent monomer is not particularly limited, but is preferably 0.1 to 20% by mass because durability is more excellent.
  • the lower limit is more preferably 0.5% by mass or more, further preferably 0.7% by mass or more, and particularly preferably 0.9% by mass or more.
  • the upper limit value is more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 8% by mass or less.
  • the content ratio of the component (a5) in the constituent monomer is not particularly limited, but is preferably 20% by mass or less.
  • the copolymer used in the present embodiment is not particularly limited, but the weight average molecular weight is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and 4,000. More preferably, it is ⁇ 20,000. When the weight average molecular weight is within the above range, a hydrophilic oil repellent excellent in hydrophilicity, oil repellency, and oil removability is easily obtained.
  • the weight average molecular weight can be measured using the GPC column chromatography method under the following conditions, and those calibrated with polyethylene glycol having molecular weights of 300, 2000, 8000, and 20000 were used as standard samples.
  • LC-10AD manufactured by Shimadzu Corporation
  • Detector RID-10A (manufactured by Shimadzu Corporation)
  • Column Concatenated Shodex GPC KF-G, KF-803, KF802.5, KF-802, KF-801 (all manufactured by Showa Denko)
  • Eluent Tetrahydrofuran Sample injection: 0.5 wt% solution, 100 ⁇ L ⁇ Flow rate: 0.8mL / min ⁇ Temperature: 25 °C
  • crosslinking agent (b) examples include a carbodiimide crosslinking agent, an oxazoline crosslinking agent, and an epoxy crosslinking agent.
  • a silane coupling agent can also be used as the crosslinking agent (b).
  • carbodiimide-based crosslinking agent examples include Nisshinbo's Carbodilite V-02, Carbodilite V-02-L2, Carbodilite E-01, Carbodilite E-02, Carbodilite E-03A, Carbodilite E-04, and the like.
  • Examples of the oxazoline-based crosslinking agent include Epocross K-2010E, Epocross K-2020E, Epocross K-2030E, Epocross WS-500, and Epocross WS-700 manufactured by Nippon Shokubai Co., Ltd.
  • epoxy crosslinking agent examples include Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622, Denacol EX-512, Denacol EX- manufactured by Nagase Chemtech Co., Ltd.
  • Epolite 400P Epolite 1500NP, Epolite 80MF, Epolite 100MF, Sakamoto Pharmaceutical Co., Ltd.
  • silane coupling agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, and ⁇ -aminopropylethoxy sold by Shin-Etsu Chemical, Nippon Unicar, Chisso, Toshiba Silicone and the like.
  • Silane N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldiethoxysilane , ⁇ -methacryloxypropyltriethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, 2- (3,4-epoxy Hexyl) ethyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltriethoxysilane, N
  • the content of the crosslinking agent (b) is not particularly limited, but is preferably 1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the constituent monomer. More preferably, it is part by mass.
  • the said crosslinking agent (b) may be used independently and may use 2 or more types together.
  • the manufacturing method of a copolymer is not specifically limited, For example, the (meth) acrylate compound (a1) which has a fluoroalkyl group, the (meth) acrylate compound (a2) which has a polyoxyalkylene group, a polymerization initiator, a solvent ( b) is mixed at least, and the mixture is heated to polymerize at least the (meth) acrylate compound (a1) having a fluoroalkyl group and the (meth) acrylate compound (a2) having a polyoxyalkylene group.
  • step A for example, (meth) acrylic acid (a3) may be added and mixed in addition to the various materials described above.
  • step B for example, a (meth) acrylate compound (a1) having a fluoroalkyl group, a (meth) acrylate compound (a2) having a polyoxyalkylene group, and (meth) acrylic acid (a3) are prepared. Polymerized.
  • the polymerization method is not particularly limited, but is preferably solution polymerization.
  • the polymerization temperature is not particularly limited, but is usually preferably in the range of 40 to 120 ° C.
  • the polymerization time is not particularly limited, but it is usually preferably about 4 to 15 hours.
  • polymerization initiator conventionally known ones can be used.
  • peroxides such as benzoyl peroxide, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, azobisisobutyrate.
  • azo compounds such as nitrile and 2,2′-azobis-2-methylbutyronitrile.
  • the amount to be used is not particularly limited, but usually 0.1 to 5 parts by mass is preferable with respect to 100 parts by mass of the constituent monomer.
  • the solvent (c) may be water or an organic solvent.
  • organic solvent include aromatic solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane and isophorone, and ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone.
  • Ester solvents such as ethyl acetate and butyl acetate, glycol ether ester solvents such as ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol di Glycol ether solvents such as butyl ether, dimethyl sulfoxide, dimethylformamide, N- Chill-2-pyrrolidone and the like, and among this, acetone, methyl ethyl ketone, ethyl acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, is preferably a diethylene glycol diethyl ether.
  • the polymer composition after polymerization can be used as it is as a hydrophilic oil repellent, or may be used as a hydrophilic oil repellent after dilution with the solvent (c) as necessary.
  • the hydrophilic oil repellent according to the present embodiment includes other hydrophilic agents, other oil repellents, water repellents, insect repellents, flame retardants, anti-wrinkle agents, antistatic agents, flexible materials, as long as they do not contradict the purpose of the invention. Finishing agents, preservatives, fragrances and antioxidants can be included as required.
  • the object to be treated with the hydrophilic oil repellent according to this embodiment is not particularly limited, and can be used for various articles including glass, plastic, metal, electronic substrate, textiles, leather, stone, wood, paper and the like.
  • a coating method such as spraying, spin coating, or dipping may be appropriately selected depending on the treatment target, and a method such as heat treatment for drying or crosslinking may be used as necessary.
  • (Meth) acrylate compound having polyoxyalkylene group (a2) (A2-1) Polyoxyethylene glycol monomethyl ether methacrylate (number of repeating units of oxyethylene group: 15) (A2-2) Polyoxyethylene glycol monomethyl ether methacrylate (number of repeating units of oxyethylene group: 23) (A2-3) Polyoxyethylene glycol monomethyl ether methacrylate (number of repeating units of oxyethylene group: 40) (A2-4) Polyoxyethylene glycol monomethyl ether methacrylate (number of repeating units of oxyethylene group: 90)
  • Alkoxysilyl group-containing (meth) acrylate (a4) (A4-1) 3-Methacryloxypropyltrimethoxysilane (trade name: KBM-503)
  • Crosslinking agent (b) (B-1) Silane coupling agent (trade names: KBM-903, 3-aminopropyltrimethoxysilane) (B-2) Carbodiimide type crosslinking agent (trade name: Carbodilite V-02-L2, 40% by mass solution) (B-3) Oxazoline-based crosslinking agent (trade name: Epocross WS-500, 39% by mass solution) (b-4) Epoxy-based crosslinking agent (trade name: Denacol EX-614B)
  • Examples 1 to 16 To a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux tube, methyl ethyl ketone as a compound (a1) to (a4) and solvent (c) are added at a mass ratio shown in Table 1, and nitrogen is added. Replacement was performed. Subsequently, t-butyl peroxypivalate (manufactured by NOF Corporation, trade name: perbutyl PV, 71% by mass solution) was added to 100 parts by mass of the total amount of the above compounds (a1) to (a4). A copolymer solution (copolymer concentration 25% by mass) was obtained by adding 1.5 parts by mass and reacting at 65 ° C. for 8 hours.
  • t-butyl peroxypivalate manufactured by NOF Corporation, trade name: perbutyl PV, 71% by mass solution
  • a hydrophilic oil repellent was prepared by adding the crosslinking agent (b) to the obtained copolymer solution at a ratio shown in Table 1, and further diluting with ethanol so that the concentration of the copolymer would be 1% by mass. .
  • This hydrophilic oil repellent was applied on an aluminum plate (1 cm ⁇ 1 cm) by a spin coating method so as to have a film thickness of 10 ⁇ m, and dried in an oven at 105 ° C. for 10 minutes to prepare a test piece.
  • Example 17 A copolymer was obtained in the same manner as in Example 11 except that the solvent (c) was changed from methyl ethyl ketone to diethylene glycol diethyl ether to prepare a test piece.
  • Example 18 After the organic solvent of the copolymer solution obtained in Example 11 (concentration of copolymer of 25% by mass) was distilled off under reduced pressure, 400 g of water was mixed to obtain a copolymer in which the solvent (c) was water. (Copolymer concentration 25% by mass) was obtained, and a test piece was prepared in the same manner as in Example 1.
  • Example 1 A test piece was prepared in the same manner as in Example 1 except that the copolymer and the crosslinking agent were not used.
  • Example 2 (Comparative Example 2) Implementation was performed except that the copolymer was synthesized using the compounds of (ac1-1) and (a4-1) in the proportions shown in Table 1 as a constituent monomer of the copolymer, and no crosslinking agent was used. A test piece was produced in the same manner as in Example 1.
  • A When immersed in water for 10 seconds, at least a part of hexadecane floats on the water surface, and when it is washed once with 2 ml of water, hexadecane does not remain on the coated surface.
  • B Hexadecane does not float on the water surface when immersed in water for 10 seconds, but when it is washed once with 2 mL of water, hexadecane does not remain on the coated surface.
  • C When immersed in water for 10 seconds and then washed twice with 2 mL of water, hexadecane does not remain on the coated surface.
  • test piece was immersed in 200 mL of water at 25 ° C. for 30 seconds, 10 minutes or 5 hours, then taken out and dried at 25 ° C. for 24 hours. Using the test piece after drying, it was evaluated by the same method as the oil removing property.
  • test piece (Durability / Abrasion resistance) The test piece was immersed in 200 mL of 25 ° C. water for 30 minutes and then taken out and dried at 25 ° C. for 24 hours. The coated surface of the test piece after drying was rubbed back and forth 30 times with a load of 100 g / cm 2 using tissue paper (Itcotish: manufactured by Itoman). Using the test piece after rubbing, it was evaluated by the same method as the oil removal property.
  • the hydrophilic oil repellent of the present invention can be suitably used as a coating agent for the purpose of antifouling the surface of the target article.

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  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un agent oléophobe hydrophile qui présente d'excellentes propriétés d'hydrophilie, d'oléophobie et d'aptitude à l'élimination d'huile. Un agent oléophobe hydrophile selon la présente invention est conçu pour contenir un copolymère qui est obtenu par polymérisation de monomères constitutifs qui contiennent au moins un composé (meth)acrylate (a1) possédant un groupe fluoroalkyle ayant de 1 à 6 atomes de carbone et un composé (méth)acrylate (a2) possédant un groupe polyoxyalkylène; et un agent de réticulation (b).
PCT/JP2019/018981 2018-06-04 2019-05-13 Agent oléophobe hydrophile WO2019235143A1 (fr)

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JP2018107241A JP2019210371A (ja) 2018-06-04 2018-06-04 親水撥油剤
JP2018-107241 2018-06-04

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Cited By (1)

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JP2020143212A (ja) * 2019-03-06 2020-09-10 第一工業製薬株式会社 含フッ素共重合体含有組成物

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JPS59204980A (ja) * 1983-05-04 1984-11-20 旭硝子株式会社 耐久性の優れた防汚加工剤
JP2003025520A (ja) * 2001-07-16 2003-01-29 Fukuvi Chem Ind Co Ltd 防汚性に優れた成形品及びその製造方法
JP2005330354A (ja) * 2004-05-19 2005-12-02 Ohara Palladium Kagaku Kk 親水・撥油加工剤ならびにそれで処理した繊維製品
JP2008308684A (ja) * 2007-05-15 2008-12-25 Fujifilm Corp 水性塗料組成物
JP2012512944A (ja) * 2008-12-18 2012-06-07 スリーエム イノベイティブ プロパティズ カンパニー コーティング組成物
JP2017105975A (ja) * 2015-11-26 2017-06-15 セントラル硝子株式会社 含フッ素単量体、含フッ素重合体およびそれを用いた親水撥油剤並びにそれを用いた基材の親水撥油化方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59204980A (ja) * 1983-05-04 1984-11-20 旭硝子株式会社 耐久性の優れた防汚加工剤
JP2003025520A (ja) * 2001-07-16 2003-01-29 Fukuvi Chem Ind Co Ltd 防汚性に優れた成形品及びその製造方法
JP2005330354A (ja) * 2004-05-19 2005-12-02 Ohara Palladium Kagaku Kk 親水・撥油加工剤ならびにそれで処理した繊維製品
JP2008308684A (ja) * 2007-05-15 2008-12-25 Fujifilm Corp 水性塗料組成物
JP2012512944A (ja) * 2008-12-18 2012-06-07 スリーエム イノベイティブ プロパティズ カンパニー コーティング組成物
JP2017105975A (ja) * 2015-11-26 2017-06-15 セントラル硝子株式会社 含フッ素単量体、含フッ素重合体およびそれを用いた親水撥油剤並びにそれを用いた基材の親水撥油化方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020143212A (ja) * 2019-03-06 2020-09-10 第一工業製薬株式会社 含フッ素共重合体含有組成物
WO2020179755A1 (fr) * 2019-03-06 2020-09-10 第一工業製薬株式会社 Composition contenant un copolymère contenant du fluor
JP7289204B2 (ja) 2019-03-06 2023-06-09 第一工業製薬株式会社 含フッ素共重合体含有組成物

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