WO2019235143A1 - Hydrophilic oil repellent agent - Google Patents

Hydrophilic oil repellent agent 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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Prior art keywords
meth
acrylate
mass
group
oil repellent
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PCT/JP2019/018981
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French (fr)
Japanese (ja)
Inventor
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/en

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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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Abstract

The present invention provides a hydrophilic oil repellent agent which has excellent hydrophilicity, oil repellency and oil removability. According to the present invention, a hydrophilic oil repellent agent contains: a copolymer which is obtained by polymerizing constituent monomers that contain at least a (meth)acrylate compound (a1) that has a fluoroalkyl group having 1-6 carbon atoms and a (meth)acrylate compound (a2) that has a polyoxyalkylene group; and a crosslinking agent (b).

Description

親水撥油剤Hydrophilic oil repellent
　本発明は、親水性、撥油性、及び油除去性に優れた親水撥油剤に関する。 The present invention relates to a hydrophilic oil repellent having excellent hydrophilicity, oil repellency, and oil removability.
　ガラス、金属、繊維等の基材表面に含フッ素化合物またはシリコーン化合物等の撥水剤を塗布して皮膜を形成することで表面を撥水性とする、撥水処理を施す方法が知られている。 There is known a method of applying a water repellency treatment to make the surface water-repellent by applying a water-repellent agent such as a fluorine-containing compound or a silicone compound to the surface of a substrate such as glass, metal or fiber to form a film. .
　また、部材表面の水に対する接触角を低下させて、部材表面を水に濡れやすい親水性とする親水性処理を施す方法も知られている。例えばガラス表面に親水性処理を施すことにより、浴室や洗面所の鏡等に防曇性を付与することができる。 Also known is a method in which the contact angle of the member surface with water is lowered to make the member surface hydrophilic so that the member surface is easily wetted with water. For example, by applying a hydrophilic treatment to the glass surface, it is possible to impart antifogging properties to a mirror in a bathroom or a bathroom.
　また、含フッ素アルキル基を有する化合物等の撥油剤を基材表面に塗布して皮膜を形成することで表面を撥油性とする撥油処理を施す方法が知られている。含フッ素アルキル基は撥油性とともに撥水性を有するものであり、その性質を用いた撥水撥油剤は従来から広く用いられている。一方、対象物の表面に親水性と撥油性を併せ持たせることのできる親水撥油剤は、表面に付着した油分を水だけで容易に洗い流すことを可能にするものであるが、十分な性能を有する親水撥油剤は未だ得られていない。 Also known is a method of applying an oil repellency treatment to make the surface oil-repellent by forming a film by applying an oil repellant such as a compound having a fluorine-containing alkyl group to the surface of the substrate. The fluorine-containing alkyl group has water repellency as well as oil repellency, and water / oil repellents using such properties have been widely used. On the other hand, 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.
　引用文献１には、このような親水性と撥油性とを併せ持つ親水撥油剤について開示されているが、実施例の記載（例えば段落０１１０）からも分かるように、汚れを除去するために水で十分に洗い流す必要があり、油除去性が不十分であった。 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.
特開２０１７－１０５９７５号公報JP 2017-105975 A
　本発明は上記に鑑みてなされたものであり、親水性、撥油性、油除去性、耐久性および耐摩耗性に優れた親水撥油剤を提供することを目的とする。 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.
　本発明の親水撥油剤は、炭素数１～６のフルオロアルキル基を有する（メタ）アクリレート化合物（ａ１）、およびポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）を少なくとも含有する構成モノマーを重合してなる共重合体と、架橋剤（ｂ）とを含有するものである。 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).
　上記成分（ａ２）は、ポリオキシアルキレングリコールモノアルキルエーテル（メタ）アクリレートであるものとすることができる。 The component (a2) may be a polyoxyalkylene glycol monoalkyl ether (meth) acrylate.
　上記成分（ａ２）のオキシアルキレン基の繰り返し単位数は、８以上１５０以下であるものとすることができる。 The number of repeating units of the oxyalkylene group in the component (a2) can be 8 or more and 150 or less.
　上記成分（ａ２）の含有割合は、上記成分（ａ１）１００質量部に対して、１００～９００質量部であるものとすることができる。 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).
　構成モノマーとして、（メタ）アクリル酸（ａ３）をさらに含有するものとすることができる。 As a constituent monomer, (meth) acrylic acid (a3) can be further contained.
　上記共重合体は、構成モノマーとして、アルコキシシリル基含有（メタ）アクリレート（ａ４）をさらに含有するものとすることができる。 The copolymer may further contain an alkoxysilyl group-containing (meth) acrylate (a4) as a constituent monomer.
　本発明の物品は、上記親水撥油剤を用いて処理されたものである。 The article of the present invention has been treated with the above hydrophilic oil repellent.
　本発明によれば、親水性、撥油性、油除去性、耐久性および耐摩耗性に優れた親水撥油剤、並びにこれを用いて処理された、防汚性や汚れ除去性に優れた物品を提供できる。 According to the present invention, a 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 therewith Can be provided.
　本実施の形態に係る親水撥油剤は、炭素数１～６のフルオロアルキル基を有する（メタ）アクリレート化合物（ａ１）、およびポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）を少なくとも含有する構成モノマーを重合してなる共重合体と、架橋剤（ｂ）とを含有するものである。なお、本発明において、「（メタ）アクリレート」は、アクリレート又はメタクリレートを意味する。 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). In the present invention, “(meth) acrylate” means acrylate or methacrylate.
　本実施の形態に係る炭素数１～６のフルオロアルキル基を有する（メタ）アクリレート化合物（ａ１）としては、例えば、フルオロアルキル（メタ）アクリレート、フルオロアルキルアルキレン（メタ）アクリレート、フルオロアルキルポリオキシフルオロアルキレン（メタ）アクリレートなどが挙げられる。これらのうち、フルオロアルキル（メタ）アクリレート、フルオロアルキルアルキレン（メタ）アクリレートが好ましく、フルオロアルキルアルキレン（メタ）アクリレートがより好ましい。上記フルオロアルキル基は、炭素数２～６のフルオロアルキル基であることが好ましく、炭素数４～６のフルオロアルキル基であることがより好ましい。また、上記フルオロアルキル基は、パーフルオロアルキル基であることが好ましい。なお、本明細書において、「（パー）フルオロ」は、パーフルオロまたはフルオロを意味する。 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. In the present specification, “(per) fluoro” means perfluoro or fluoro.
　フルオロアルキル（メタ）アクリレートとしては、例えば、（パー）フルオロメチル（メタ）アクリレート、（パー）フルオロエチル（メタ）アクリレート、（パー）フルオロプロピル（メタ）アクリレート、（パー）フルオロブチル（メタ）アクリレート、（パー）フルオロペンチル（メタ）アクリレート、（パー）フルオロヘキシル（メタ）アクリレートなどが挙げられる。なお、フルオロアルキル（メタ）アクリレートは、下記一般式（１）で表すこともできる。
　　Ｒｆ－Ｏ－Ｘ　・・・（１）
　ただし、Ｒｆはフルオロアルキル基であり、Ｘはアクリロイル基またはメタクリロイル基である。 Examples of fluoroalkyl (meth) acrylates 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. In addition, fluoroalkyl (meth) acrylate can also be represented by the following general formula (1).
Rf-OX (1)
However, Rf is a fluoroalkyl group and X is an acryloyl group or a methacryloyl group.
　フルオロアルキルアルキレン（メタ）アクリレートとしては、例えば、（パー）フルオロメチルメチレン（メタ）アクリレート、（パー）フルオロメチルエチレン（メタ）アクリレート、（パー）フルオロエチルメチレン（メタ）アクリレート、（パー）フルオロエチルエチレン（メタ）アクリレート、（パー）フルオロプロピルメチレン（メタ）アクリレート、（パー）フルオロプロピルエチレン（メタ）アクリレート、（パー）フルオロブチルメチレン（メタ）アクリレート、（パー）フルオロブチルエチレン（メタ）アクリレート、（パー）フルオロペンチルメチレン（メタ）アクリレート、（パー）フルオロペンチルエチレン（メタ）アクリレート、（パー）フルオロヘキシルメチレン（メタ）アクリレート、（パー）フルオロヘキシルエチレン（メタ）アクリレートなどが挙げられる。なお、フルオロアルキルアルキレン（メタ）アクリレートは、下記一般式（２）で表すこと
もできる。
　　Ｒｆ－Ｙ－Ｏ－Ｘ　・・・（２）
　ただし、Ｒｆはフルオロアルキル基であり、Ｙはアルキレン基であり、Ｘはアクリロイル基またはメタクリロイル基である。 Examples of the fluoroalkylalkylene (meth) acrylate include (per) fluoromethylmethylene (meth) acrylate, (per) fluoromethylethylene (meth) acrylate, (per) fluoroethylmethylene (meth) acrylate, and (per) fluoroethyl. Ethylene (meth) acrylate, (per) fluoropropylmethylene (meth) acrylate, (per) fluoropropylethylene (meth) acrylate, (per) fluorobutylmethylene (meth) acrylate, (per) fluorobutylethylene (meth) acrylate, (Per) fluoropentylmethylene (meth) acrylate, (per) fluoropentylethylene (meth) acrylate, (per) fluorohexylmethylene (meth) acrylate, (per) fluorohex Such Ruechiren (meth) acrylate. In addition, fluoroalkyl alkylene (meth) acrylate can also be represented by the following general formula (2).
Rf-YOX (2)
However, Rf is a fluoroalkyl group, Y is an alkylene group, X is an acryloyl group or a methacryloyl group.
　フルオロアルキルポリオキシフルオロアルキレン（メタ）アクリレートとしては、例えば、（パー）フルオロメチルポリオキシフルオロエチレン（メタ）アクリレート、（パー）フルオロエチルポリオキシフルオロエチレン（メタ）アクリレート、（パー）フルオロプロピルポリオキシフルオロエチレン（メタ）アクリレート、（パー）フルオロブチルポリオキシフルオロエチレン（メタ）アクリレート、（パー）フルオロペンチルポリオキシフルオロエチレン（メタ）アクリレート、（パー）フルオロヘキシルポリオキシフルオロエチレン（メタ）アクリレート、（パー）フルオロヘキシルポリオキシフルオロプロピレン（メタ）アクリレートなどが挙げられる。なお、フルオロアルキルポリオキシフルオロアルキレン（メタ）アクリレートは、下記一般式（３）で表すこともできる。
　　Ｒｆ－Ｚ－Ｏ－Ｘ　・・・（３）
　ただし、Ｒｆはフルオロアルキル基であり、Ｚはポリオキシフルオロアルキレン基である、Ｘはアクリロイル基またはメタクリロイル基である。 Examples of the fluoroalkyl polyoxyfluoroalkylene (meth) acrylate 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. In addition, fluoroalkyl polyoxyfluoroalkylene (meth) acrylate can also be represented by the following general formula (3).
Rf-Z-OX (3)
However, Rf is a fluoroalkyl group, Z is a polyoxyfluoroalkylene group, X is an acryloyl group or a methacryloyl group.
　本実施の形態に係るポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）としては、例えば、下記一般式（４）で表されるものが挙げられる。なお、成分（ａ１）に該当するものは除く。
　　Ｒ１－Ｏ－（ＹＯ）ｎ－Ｘ　・・・（４）
　ただし、Ｒ１は水素原子、又は炭素原子数１～６のアルキル基であり、Ｙはアルキレン基であり、ｎは２以上の整数であり、Ｘはアクリロイル基またはメタクリロイル基である。 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). In addition, the thing applicable to a component (a1) is excluded.
R 1 —O— (YO) n —X (4)
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, and X is an acryloyl group or a methacryloyl group.
　上記一般式（４）中のＲ１は、炭素数１～６のアルキル基であることが好ましい。一般式（４）の化合物としては、ポリオキシアルキレングリコールモノアルキルエーテル（メタ）アクリレートであることが好ましく、ポリオキシエチレングリコールモノメチルエーテルメタクリレートであることがさらに好ましい。 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.
　上記一般式（４）中のアルキレン基としては、油除去性がより優れることから、炭素数１～２０の直鎖または分岐のアルキレン基であることが好ましく、炭素数１～１０であることがより好ましく、炭素数１～５であることがさらに好ましく、炭素数２～４が特に好ましい。具体的には、メチレン基、エチレン基、プロピレン基、ブチレン基等が挙げられ、これらのアルキレン基は、ハロゲン以外の置換基を有するものであってもよい。これらのうち、エチレン基、プロピレン基が好ましく、エチレン基がより好ましい。また、ポリオキシアルキレン基としては、これらのアルキレン基のうちの１種が重合したものであってもよく、２種以上が重合したものであってもよい。２種以上のアルキレン基が重合する場合、ランダム重合であってもよく、ブロック重合であってもよい。 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.
　上記一般式（４）中のオキシアルキレン基の繰り返し単位数ｎは、特に限定されないが、油除去性および耐久性がより優れることから、８以上１５０以下であることが好ましい。下限値は、１０以上であることがより好ましく、１５以上であることがさらに好ましい。上限値は、１２０以下であることがより好ましく、１００以下であることがさらに好ましい。 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.
　上記成分（ａ２）の含有割合は、特に限定されないが、油除去性および耐久性がより優れることから、上記成分（ａ１）１００質量部に対して、１００～９００質量部であることが好ましい。下限値は、２００質量部以上であることがより好ましく、３００質量部以上であることがさらに好ましい。上限値は、７５０質量部以下であることがより好ましく、６００質量部以下であることがさらに好ましい。 Although 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.
　上記構成モノマーは、耐久性を向上させる観点から、さらに（ａ３）（メタ）アクリル酸を含むことが好ましい。このような化合物としては、アクリル酸、メタアクリル酸が挙げられる。 The above constituent monomer preferably further includes (a3) (meth) acrylic acid from the viewpoint of improving durability. Examples of such a compound include acrylic acid and methacrylic acid.
　上記成分（ａ３）の含有割合は、特に限定されないが、油除去性および耐久性がより優れることから、成分（ａ１）１００質量部に対して、１～５０質量部であることが好ましい。下限値は、２質量部以上であることがより好ましく、３質量部以上であることがさらに好ましい。上限値は、３０質量部以下であることがより好ましい。 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.
　また上記成分（ａ３）の含有割合は、特に限定されないが、油除去性および耐久性がより優れることから、成分（ａ２）１００質量部に対して、０．５～２０質量部であることが好ましい。下限値は、１質量部以上であることがより好ましい。上限値は、１５質量部以下であることがより好ましく、１０質量部以下であることがさらに好ましい。 Further, 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.
　上記構成モノマーは、耐久性を向上させる観点から、さらに（ａ４）アルコキシシリル基含有（メタ）アクリレートを含むことが好ましい。このような化合物としては、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシランなどが挙げられる。 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.
　上記成分（ａ４）の含有割合は、特に限定されないが、耐久性がより優れることから、成分（ａ１）１００質量部に対して、１～６０質量部であることが好ましい。下限値は、２質量部以上であることがより好ましく、３質量部以上であることがさらに好ましい。上限値は、４０質量部以下であることがより好ましく、３０質量部以下であることがさらに好ましい。 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.
　また上記成分（ａ４）の含有割合は、特に限定されないが、耐久性がより優れることから、成分（ａ２）１００質量部に対して、０．５～２０質量部であることが好ましい。下限値は、１質量部以上であることがより好ましい。上限値は、１５質量部以下であることがより好ましい。 Further, 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.
　上記構成モノマーは、発明の目的に反しない範囲で、上記成分（ａ１）～（ａ４）以外に、（メタ）アクリレート化合物（ａ５）をさらに含んでいてもよい。このような化合物としては、例えば、アルキル（メタ）アクリレート、オキシアルキレン基含有（メタ）アクリレートモノマーなどが挙げられる。 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. Examples of such compounds include alkyl (meth) acrylates, oxyalkylene group-containing (meth) acrylate monomers, and the like.
　アルキル（メタ）アクリレートとしては、例えば、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、イソアミル（メタ）アクリレートが挙げられる。 Examples of the alkyl (meth) acrylate include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth). Examples include acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and isoamyl (meth) acrylate.
　オキシアルキレン基含有（メタ）アクリレートモノマーとしては、例えば、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリ
コールジ（メタ）アクリレート、ビスフェノールＡエチレンオキサイド付加物ジ（メタ）アクリレートなどが挙げられる。 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.
　また、グリシジル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、（メタ）アクリル酸アミド、Ｎ－メチロール（メタ）アクリル酸アミド、ジアセトン（メタ）アクリル酸アミド、イソシアネートエチル（メタ）アクリレート、ポリシロキサンを有する（メタ）アクリレート、２－メタクロイロキシエチルアシッドホスフェート、ジメチルアミノメチル（メタ）アクリレートなども使用できる。 In addition, 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.
　構成モノマー中の成分（ａ１）の含有割合は、特に限定されないが、油除去性および耐久性がより優れることから、５～５０質量％であることが好ましい。下限値は、１０質量％以上であることが好ましく、１５質量％以上であることがさらに好ましい。上限値は、４０質量％以下であることがより好ましく、３０質量％以下であることがさらに好ましい。 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.
　構成モノマー中の成分（ａ２）の含有割合は、特に限定されないが、油除去性および耐久性がより優れることから、４０～９５質量％であることが好ましい。下限値は、５０質量％以上であることがより好ましく、６０質量％以上であることがさらに好ましい。上限値は、９４．９質量％以下であることがより好ましく、９４．５質量％以下であることがさらに好ましく、特に、９０質量％以下であることが好ましく、８５質量％以下であることがより好ましく、８０質量％以下であることがさらに好ましい。 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.
　構成モノマー中の成分（ａ３）の含有割合は、特に限定されないが、耐久性がより優れることから、０．１～２０質量％であることが好ましい。下限値は、０．５質量％以上であることがより好ましく、０．７質量％以上であることがさらに好ましく、０．９質量％以上であることが特に好ましい。上限値は、１５質量％以下であることがより好ましく、１０質量％以下であることがさらに好ましく、８質量％以下であることが特に好ましい。 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.
　構成モノマー中の成分（ａ４）の含有割合は、特に限定されないが、耐久性がより優れることから、０．１～２０質量％であることが好ましい。下限値は、０．５質量％以上であることがより好ましく、０．７質量％以上であることがさらに好ましく、０．９質量％以上であることが特に好ましい。上限値は、１５質量％以下であることがより好ましく、１０質量％以下であることがさらに好ましく、８質量％以下であることが特に好ましい。 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.
　構成モノマー中の成分（ａ５）の含有割合は、特に限定されないが、２０質量％以下であることが好ましい。 The content ratio of the component (a5) in the constituent monomer is not particularly limited, but is preferably 20% by mass or less.
　本実施の形態で用いる共重合体は、特に限定されないが、重量平均分子量が２，０００～１００，０００であることが好ましく、３，０００～５０，０００であることがより好ましく、４，０００～２０，０００であることがさらに好ましい。重量平均分子量が上記範囲内であると、親水性、撥油性、及び油除去性に優れた親水撥油剤が得られやすい。なお、重量平均分子量は、ＧＰＣカラムクロマトグラフィ法を用いて、下記の条件で測定することができ、標準サンプルとして分子量３００、２０００、８０００、及び２００００のポリエチレングリコールで校正したものを用いた。 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.
・装置：ＬＣ－１０ＡＤ（島津製作所社製）
・検出器：ＲＩＤ－１０Ａ（島津製作所社製）
・カラム：Ｓｈｏｄｅｘ　ＧＰＣ　ＫＦ－Ｇ、ＫＦ－８０３、ＫＦ８０２．５、ＫＦ－８０２、ＫＦ－８０１を連結したもの（いずれも昭和電工社製）
・溶離液：テトラヒドロフラン
・サンプル注入：０．５重量％溶液、１００μＬ
・流速：０．８ｍＬ／ｍｉｎ
・温度：２５℃ ・ Device: 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 μL
・ Flow rate: 0.8mL / min
・ Temperature: 25 ℃
　架橋剤（ｂ）としては、例えば、カルボジイミド系架橋剤、オキサゾリン系架橋剤、エポキシ系架橋剤などが挙げられる。また、シランカップリング剤も架橋剤（ｂ）として使用することができる。 Examples of the crosslinking agent (b) 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).
　上記カルボジイミド系架橋剤としては、例えば、日清紡社製のカルボジライトＶ－０２、カルボジライトＶ－０２－Ｌ２、カルボジライトＥ－０１、カルボジライトＥ－０２、カルボジライトＥ－０３Ａ、カルボジライトＥ－０４などが挙げられる。 Examples of the carbodiimide-based crosslinking agent 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.
　上記オキサゾリン系架橋剤としては、例えば、日本触媒社製のエポクロスＫ－２０１０Ｅ、エポクロスＫ－２０２０Ｅ、エポクロスＫ－２０３０Ｅ、エポクロスＷＳ－５００、エポクロスＷＳ－７００などが挙げられる。 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.
　エポキシ系架橋剤としては、例えば、ナガセケムテック（株）製のデナコールＥＸ－６１１、デナコールＥＸ－６１２、デナコールＥＸ－６１４、デナコールＥＸ－６１４Ｂ、デナコールＥＸ－６２２、デナコールＥＸ－５１２、デナコールＥＸ－５２１、デナコールＥＸ－４１１、デナコールＥＸ－４２１、デナコールＥＸ－３０１、デナコールＥＸ－３１３、デナコールＥＸ－３１４、デナコールＥＸ－３２１、デナコールＥＸ－２１１、デナコールＥＸ－８１０、デナコールＥＸ－８１１、デナコールＥＸ－８５１、デナコールＥＸ－８２１、デナコールＥＸ－８３０、デナコールＥＸ－８３２、デナコールＥＸ－８４１、デナコールＥＸ－８６１、デナコールＥＸ－９１１、デナコールＥＸ－９４１、デナコールＥＸ－９２０、デナコールＥＸ－９２１、デナコールＥＸ－９３１、デナコールＥＸ－１４５、デナコールＥＸ－１７１、デナコールＥＸ－７０１、共栄社化学（株）製のエポライト４０Ｅ、エポライト１００Ｅ、エポライト２００Ｅ、エポライト４００Ｅ、エポライト７０Ｐ、エポライト２００Ｐ、エポライト４００Ｐ、エポライト１５００ＮＰ、エポライト８０ＭＦ、エポライト１００ＭＦ、坂本薬品工業（株）製のＳＲ－ＮＰＧ、ＳＲ－１６Ｈ、ＳＲ－ＴＭＰ、ＳＲ－ＴＰＧ、ＳＲ－４ＰＧ、ＳＲ－２ＥＧ、ＳＲ－８ＥＧ、ＳＲ－８ＥＧＳ、ＳＲ－ＧＬＧ、ＳＲ－ＤＧＥ、ＳＲ－４ＧＬ、ＳＲ－４ＧＬＳ、日本油脂（株）製のエピオールＢＥ－２００、エピオールＧ－１００、エピオールＥ－１００、エピオールＥ－４００、エピオールＥ－１０００、エピオールＰ－２００、エピオールＮＰＧ－１００、エピオールＴＭＰ－１００、エピオールＯＨなどが挙げられる。 Examples of the epoxy crosslinking agent 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. 521, Denacol EX-411, Denacol EX-421, Denacol EX-301, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-211, Denacol EX-810, Denacol EX-811, Denacol EX- 851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacor Cole EX-921, Denacol EX-931, Denacol EX-145, Denacol EX-171, Denacol EX-701, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, manufactured by Kyoeisha Chemical Co., Ltd. Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 100MF, Sakamoto Pharmaceutical Co., Ltd. SR-NPG, SR-16H, SR-TMP, SR-TPG, SR-4PG, SR-2EG, SR-8EG, SR- 8EGS, SR-GLG, SR-DGE, SR-4GL, SR-4GLS, Epiol BE-200, Epiol G-100, Epiol E-100, Epiol E-400, Epiol E-1000, manufactured by NOF Corporation Pioru P-200, EPIOL NPG-100, EPIOL TMP-100, and the like Epiol OH.
　上記シランカップリング剤としては、例えば、信越化学工業、日本ユニカー、チッソ、東芝シリコーン等から販売されているビニルトリメトキシシラン、ビニルトリエトキシシラン、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルエトキシシラン、Ｎ－〔２－（ビニルベンジルアミノ）エチル〕－３－アミノプロピルトリメトキシシラン、γ－メタクリロキシプロピルメチルジメトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルメチルジエトキシシラン、γ－メタクリロキシプロピルトリエトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、Ｎ－β（アミノエチル）γ－アミノプロピルトリメトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルトリエトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルメチルジメトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、γ－メルカブトプロピルトリメトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジメトキシジフェニルシラン、ｎ－プロピルト
リメトキシシラン、ヘキシルトリメトキシシラン、デシルトリメトキシシラン、１，６－ビス（トリメトキシシリル）ヘキサン、トリフルオロプロピルトリメトキシシラン、テトラエトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ｎ－プロピルトリエトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、ヘキサメチルジシラザン等が挙げられる。 Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropylethoxy sold by Shin-Etsu Chemical, Nippon Unicar, Chisso, Toshiba Silicone and the like. Silane, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane , Γ-methacryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxy Hexyl) ethyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ- Aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, dimethoxydiphenylsilane, n-propyltrimethoxy Silane, hexyltrimethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysila , Phenyltriethoxysilane, n- propyl triethoxysilane, hexyl triethoxysilane, octyltriethoxysilane, hexamethyldisilazane, and the like.
　上記架橋剤（ｂ）の含有割合は、特に限定されないが、構成モノマー１００質量部に対して、１～３０質量部であることが好ましく、１～２０質量部であることが好ましく、１～１５質量部であることがより好ましい。上記架橋剤（ｂ）は、単独で用いてもよく、２種以上を併用してもよい。 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.
　次に本実施の形態に係る親水撥油剤に用いる共重合体の製造方法を説明する。共重合体の製造方法は、特に限定されないが、例えば、フルオロアルキル基を有する（メタ）アクリレート化合物（ａ１）、ポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）、重合開始剤、溶剤（ｂ）を少なくとも混合する工程Ａと、この混合物を加熱して、フルオロアルキル基を有する（メタ）アクリレート化合物（ａ１）とポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）とを少なくとも重合させる工程Ｂと、得られた共重合体と架橋剤（ｂ）とを混合する工程Ｃとを有するものとすることができる。なお、上記工程Ａにおいては、たとえば、上記の各種材料の他に、（メタ）アクリル酸（ａ３）を加えて混合しても良い。この場合、上記工程Ｂにおいては、たとえば、フルオロアルキル基を有する（メタ）アクリレート化合物（ａ１）とポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）と（メタ）アクリル酸（ａ３）とが重合される。 Next, a method for producing a copolymer used for the hydrophilic oil repellent according to this embodiment will be described. Although 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. It can have the process B and the process C which mixes the obtained copolymer and a crosslinking agent (b). In step A, for example, (meth) acrylic acid (a3) may be added and mixed in addition to the various materials described above. In this case, in the 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.
　重合方法は、特に限定されないが、溶液重合であることが好ましい。重合温度は、特に限定されないが、通常は４０～１２０℃の範囲が好ましい。重合時間は、特に限定されないが、通常は４～１５時間程度であることが好ましい。 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.
　重合開始剤としては、従来公知のものを使用でき、例えば、過酸化ベンゾイル、ｔ－ブチルパーオキシピバレート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート等の過酸化物、アゾビスイソブチロニトリル、２，２’－アゾビス－２－メチルブチロニトリル等のアゾ化合物等が挙げられる。その使用量は特に限定されないが、通常は、構成モノマー１００質量部に対して、０．１～５質量部が好ましい。 As the polymerization initiator, conventionally known ones can be used. For example, peroxides such as benzoyl peroxide, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, azobisisobutyrate. And 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.
　溶剤（ｃ）は、水であってもよく、有機溶剤であってもよい。有機溶剤としては、例えば、トルエン、キシレンなどの芳香族系溶剤、ヘキサンなどの脂肪族炭化水素系溶剤、シクロヘキサン、イソホロンなどの脂環族炭化水素系溶剤、アセトン、メチルエチルケトン、シクロヘキサノンなどのケトン系溶剤、酢酸エチル、酢酸ブチルなどのエステル系溶剤、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなどのグリコールエーテルエステル系溶剤、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールジブチルエーテルなどのグリコールエーテル系溶剤、ジメチルスルホキシド、ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン等が挙げられ、この中でも、アセトン、メチルエチルケトン、酢酸エチル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテルであることが好ましい。 The solvent (c) may be water or an organic solvent. Examples of the 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.
　重合後のポリマー組成物は、そのまま親水撥油剤として使用することもでき、必要に応じて上記溶剤（ｃ）で希釈してから親水撥油剤として使用してもよい。 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.
　本実施の形態に係る親水撥油剤には、発明の目的に反しない範囲で、他の親水剤、その他の撥油剤、撥水剤、防虫剤、難燃剤、防シワ剤、帯電防止剤、柔軟仕上げ剤、防腐剤、芳香剤、酸化防止剤を必要に応じて含有させることができる。 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.
　本実施の形態に係る親水撥油剤による処理対象は特に限定されず、ガラス、プラスチック、金属、電子基板、繊維製品、皮革、石材、木材、紙等を含む種々の物品に使用することができる。処理対象に応じて、スプレー、スピンコート、浸漬等の塗布方法を適宜選択し、必要に応じて加熱処理して乾燥や架橋させる等の方法を用いることができる。 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.
　以下、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、以下の実施例及び比較例において、「部」又は「％」とあるのは特に指定しない限り、質量基準とする。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In the following examples and comparative examples, “part” or “%” is based on mass unless otherwise specified.
（使用原料）
炭素数１～６のフルオロアルキル基を有する（メタ）アクリレート化合物（ａ１）
（ａ１－１）パーフルオロヘキシルエチルメタクリレート
（ａ１－２）パーフルオロブチルエチルメタクリレート (Raw material)
(Meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms
(A1-1) Perfluorohexylethyl methacrylate (a1-2) Perfluorobutylethyl methacrylate
ポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）
（ａ２－１）ポリオキシエチレングリコールモノメチルエーテルメタクリレート（オキシエチレン基の繰り返し単位数：１５）
（ａ２－２）ポリオキシエチレングリコールモノメチルエーテルメタクリレート（オキシエチレン基の繰り返し単位数：２３）
（ａ２－３）ポリオキシエチレングリコールモノメチルエーテルメタクリレート（オキシエチレン基の繰り返し単位数：４０）
（ａ２－４）ポリオキシエチレングリコールモノメチルエーテルメタクリレート（オキシエチレン基の繰り返し単位数：９０） (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)
上記成分（ａ１）及び（ａ２）以外の（メタ）アクリレート化合物（ａ３）
（ａ３－１）アクリル酸
（ａ３－２）メタクリル酸 (Meth) acrylate compounds (a3) other than the above components (a1) and (a2)
(A3-1) Acrylic acid (a3-2) Methacrylic acid
アルコキシシリル基含有（メタ）アクリレート（ａ４）
（ａ４－１）３－メタクリロキシプロピルトリメトキシシラン（商品名：ＫＢＭ－５０３） Alkoxysilyl group-containing (meth) acrylate (a4)
(A4-1) 3-Methacryloxypropyltrimethoxysilane (trade name: KBM-503)
架橋剤（ｂ）
（ｂ－１）シランカップリング剤（商品名：ＫＢＭ－９０３、３－アミノプロピルトリメトキシシラン）
（ｂ－２）カルボジイミド系架橋剤（商品名：カルボジライトＶ－０２－Ｌ２、４０質量％溶液）
（ｂ－３）オキサゾリン系架橋剤（商品名：エポクロスＷＳ－５００、３９質量％溶液）（ｂ－４）エポキシ系架橋剤（商品名：デナコールＥＸ－６１４Ｂ） 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)
溶剤（ｃ）
（ｃ－１）メチルエチルケトン
（ｃ－２）ジエチレングリコールジエチルエーテル
（ｃ－３）水 Solvent (c)
(C-1) methyl ethyl ketone (c-2) diethylene glycol diethyl ether (c-3) water
その他
（ａｃ１－１）トリフルオロエトキシエトキシメチルアクリルアミド Other (ac1-1) trifluoroethoxyethoxymethylacrylamide
（実施例１～１６）
　撹拌機、温度計、窒素導入管及び還流管を備えた反応容器に、表１に記載の質量割合で、（ａ１）～（ａ４）の化合物、及び、溶剤（ｃ）としてメチルエチルケトンを加え、窒素置換を行った。続いて、ｔ－ブチルパーオキシピバレート（日油（株）製、商品名：パーブチルＰＶ、７１質量％溶液）を、上記（ａ１）～（ａ４）の化合物の合計量１００質量部に対して１．５質量部となるように加え、６５℃で８時間反応させることにより、共重合体溶液（共重合体の濃度２５質量％）を得た。 (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.
　得られた共重合体溶液に、表１に記載の割合で架橋剤（ｂ）を加え、さらに共重合体の濃度が１質量％となるようにエタノールで希釈することにより親水撥油剤を作製した。 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. .
　この親水撥油剤を、アルミ板（１ｃｍ×１ｃｍ）上に膜厚１０μｍとなるようにスピンコート法により塗布し、１０５℃のオーブンで１０分間乾燥することにより、試験片を作製した。 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 μm, and dried in an oven at 105 ° C. for 10 minutes to prepare a test piece.
（実施例１７）
　溶剤（ｃ）を、メチルエチルケトンからジエチレングリコールジエチルエーテルに変更した以外は、実施例１１と同様の方法により、共重合体を得て、試験片を作製した。 (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.
（実施例１８）
　実施例１１で得られた共重合体溶液（共重合体の濃度２５質量％）の有機溶剤を減圧留去した後、水４００ｇを混合することにより、溶剤（ｃ）が水である共重合体（共重合体の濃度２５質量％）を得て、実施例１と同様の方法により試験片を作製した。 (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.
（比較例１）
　共重合体および架橋剤を用いない以外は、実施例１と同様の方法により試験片を作製した。 (Comparative 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.
（比較例２）
　共重合体の構成モノマーとして、（ａｃ１－１）及び（ａ４－１）の化合物を表１に記載の割合で用いて共重合体を合成すること、および架橋剤を用いないこと以外は、実施例１と同様の方法により試験片を制作した。 (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.
　上記試験片を用いて、接触角（水およびヘキサデカン）、油除去性、耐久性および耐摩耗性を下記の方法により評価した。結果を表１に示す。 The contact angle (water and hexadecane), oil removability, durability, and wear resistance were evaluated by the following methods using the above test pieces. The results are shown in Table 1.
（接触角）
　接触角測定装置（協和界面科学社製、商品名：接触角計Ｄｒｏｐ　Ｍａｓｔｅｒ　５００）を用いて、塗布面における水およびヘキサデカンの接触角を測定し下記の基準で評価した。なお、水の液滴容量は２μＬ、ヘキサデカンの液滴容量は４μＬとし、滴下３０秒後の接触角を測定した。 (Contact angle)
Using a contact angle measurement device (Kyowa Interface Science Co., Ltd., trade name: Contact Angle Meter Drop Master 500), the contact angles of water and hexadecane on the coated surface were measured and evaluated according to the following criteria. The water droplet volume was 2 μL, the hexadecane droplet volume was 4 μL, and the contact angle 30 seconds after dropping was measured.
＜水の接触角＞
　　Ａ：３０°未満
　　Ｂ：３０°以上４０°未満
　　Ｃ：４０°以上６０°未満
　　Ｄ：６０°以上８０°未満
　　Ｅ：８０°以上 <Water contact angle>
A: Less than 30 ° B: 30 ° or more and less than 40 ° C: 40 ° or more and less than 60 ° D: 60 ° or more and less than 80 ° E: 80 ° or more
＜ヘキサデカンの接触角＞
　　Ａ：６０°以上
　　Ｂ：５０°以上６０°未満
　　Ｃ：４０°以上５０°未満
　　Ｄ：３０°以上４０°未満
　　Ｅ：３０°未満 <Contact angle of hexadecane>
A: 60 ° or more B: 50 ° or more and less than 60 ° C: 40 ° or more and less than 50 ° D: 30 ° or more and less than 40 ° E: Less than 30 °
（油除去性）
塗布面にヘキサデカン０．０２ｇを滴下した。これを、塗布面が上になるように２５℃の水６０ｍＬに１０秒間浸漬したあと取り出し、水面へのヘキサデカンの浮き上がりの有無を確認した。また、ヘキサデカンが塗布面に残っている場合はさらに水２ｍＬで洗い流し、ヘキサデカンの有無を確認することを最大３回繰り返した。 (Oil removal)
0.02 g of hexadecane was dropped onto the coated surface. This was dipped in 60 mL of 25 ° C. water for 10 seconds so that the coated surface was on top, and then taken out, and the presence or absence of hexadecane floating on the water surface was confirmed. Further, when hexadecane remained on the coated surface, it was further washed with 2 mL of water, and the presence or absence of hexadecane was confirmed up to three times.
　　Ａ：水に１０秒間浸漬した場合に少なくとも一部のヘキサデカンが水面に浮き上がり、さらに水２ｍｌで１回洗い流すと塗布面にヘキサデカンが残らない。
　　Ｂ：水に１０秒間浸漬した場合にヘキサデカンは水面に浮き上がらないが、さらに水２ｍLで１回洗い流すと塗布面にヘキサデカンが残らない。
　　Ｃ：水に１０秒間浸漬し、さらに水２ｍLで２回洗い流すと塗布面にヘキサデカンが
残らない。
　　Ｄ：水に１０秒間浸漬し、さらに水２ｍLで３回洗い流すと塗布面にヘキサデカンが
残らない。
　　Ｅ：水に１０秒間浸漬し、さらに水２ｍLで３回洗い流しても塗布面にヘキサデカン
が残る。 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.
D: Hexadecane does not remain on the coated surface when immersed in water for 10 seconds and further washed 3 times with 2 mL of water.
E: Hexadecane remains on the coated surface even after being immersed in water for 10 seconds and further washed with 2 mL of water three times.
（耐久性）
　試験片を２５℃の水２００ｍＬに、３０秒間、１０分間または５時間浸漬したあと取り出し、２５℃で２４時間乾燥させた。乾燥後の試験片を用いて、油除去性と同じ方法で評価した。 (durability)
The 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.
（耐摩耗性）
　試験片の塗布面を、ティッシュペーパー（イットコティッシュ：イトマン社製）を用いて１００ｇ／ｃｍ２の加重で３０往復摩擦した。摩擦後の試験片を用いて、油除去性と同じ方法で評価した。 (Abrasion resistance)
The coated surface of the test piece was rubbed back and forth 30 times with a load of 100 g / cm 2 using tissue paper (Itcotish: made by Itoman). Using the test piece after rubbing, it was evaluated by the same method as the oil removal property.
（耐久・耐摩耗性）
　試験片を２５℃の水２００ｍＬに３０分間浸漬したあと取り出し、２５℃で２４時間乾燥させた。乾燥後の試験片の塗布面を、ティッシュペーパー（イットコティッシュ：イトマン社製）を用いて１００ｇ／ｃｍ２の加重で３０往復摩擦した。摩擦後の試験片を用いて、油除去性と同じ方法で評価した。 (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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示された結果から、実施例の組成物は、比較例１の組成物、および比較例２の組成物と比較して、いずれも親水性、撥油性、油除去性、耐久性および耐摩耗が顕著に優れていることが分かる。また、実施例２，８～１０の結果から、（ａ２）ポリオキシアルキレン基を有する（メタ）アクリレート化合物におけるオキシアルキレン基の繰り返し単位数が大きい場合、耐久性および耐摩耗性が向上することが分かる。 From the results shown in Table 1, the compositions of the examples were all hydrophilic, oil repellent, oil-removable, durable, and compared with the compositions of Comparative Example 1 and Comparative Example 2. It can be seen that the wear resistance is remarkably excellent. Further, from the results of Examples 2 and 8 to 10, when the number of repeating units of the oxyalkylene group in the (a2) (meth) acrylate compound having a polyoxyalkylene group is large, durability and wear resistance are improved. I understand.
　本発明の親水撥油剤は、対象物品の表面の防汚等を目的としたコーティング剤として好適に用いることができる。 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.

Claims (7)

  1. 　炭素数１～６のフルオロアルキル基を有する（メタ）アクリレート化合物（ａ１）、およびポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）を少なくとも含有する構成モノマーを重合してなる共重合体と、
    架橋剤（ｂ）とを含有する、親水撥油剤。     A copolymer obtained by polymerizing 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; ,
    A hydrophilic oil repellent containing a crosslinking agent (b).
  2. 　前記ポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）が、ポリオキシアルキレングリコールモノアルキルエーテル（メタ）アクリレートであることを特徴とする、請求項１に記載の親水撥油剤。 The hydrophilic oil repellent according to claim 1, wherein the (meth) acrylate compound (a2) having a polyoxyalkylene group is a polyoxyalkylene glycol monoalkyl ether (meth) acrylate.
  3. 　前記ポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）のオキシアルキレン基の繰り返し単位数が、８以上１５０以下であることを特徴とする、請求項１又は２に記載の親水撥油剤。 The hydrophilic oil repellent according to claim 1 or 2, wherein the number of repeating units of the oxyalkylene group of the (meth) acrylate compound (a2) having a polyoxyalkylene group is 8 or more and 150 or less.
  4. 　前記ポリオキシアルキレン基を有する（メタ）アクリレート化合物（ａ２）の含有割合が、前記炭素数１～６のフルオロアルキル基を有する（メタ）アクリレート化合物（ａ１）１００質量部に対して、１００～９００質量部であることを特徴とする、請求項１～３のいずれか１項に記載の親水撥油剤。 The content ratio of the (meth) acrylate compound (a2) having a polyoxyalkylene group is 100 to 900 with respect to 100 parts by mass of the (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms. The hydrophilic oil repellent according to any one of claims 1 to 3, wherein the hydrophilic oil repellent is one part by mass.
  5. 　前記共重合体が、構成モノマーとして、（メタ）アクリル酸（ａ３）をさらに含有することを特徴とする、請求項１～４のいずれか１項に記載の親水撥油剤。 The hydrophilic oil repellent according to any one of claims 1 to 4, wherein the copolymer further contains (meth) acrylic acid (a3) as a constituent monomer.
  6. 　前記共重合体が、構成モノマーとして、アルコキシシリル基含有（メタ）アクリレート（ａ４）をさらに含有することを特徴とする、請求項１～５のいずれか１項に記載の親水撥油剤。 The hydrophilic oil repellent according to any one of claims 1 to 5, wherein the copolymer further contains an alkoxysilyl group-containing (meth) acrylate (a4) as a constituent monomer.
  7. 　請求項１～６のいずれか１項に記載の親水撥油剤を用いて処理された物品。
          An article treated with the hydrophilic oil repellent according to any one of claims 1 to 6.
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