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• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • 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
  • 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
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
• • 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
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/26—Elastomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2321/00—Characterised by the use of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2433/04—Characterised by the use 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; Derivatives of such polymers esters
  • C08J2433/14—Characterised by the use 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; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
  • C08J2433/16—Homopolymers or copolymers of esters containing halogen atoms

Definitions

• the present invention relates to a flexible water-repellent oil-repellent agent containing a fluorine-containing polymer as an active ingredient. More specifically, flexible water repellency containing a fluorine-containing polymer, which is a copolymer of a (meth) acrylic acid derivative containing a perfluoroalkyl group having 6 or less carbon atoms, which is said to have low bioaccumulation, as an active ingredient. Regarding oil repellents.
• the expression of water and oil repellency of the perfluoroalkyl group [Rf] -containing (meth) acrylate in the surface treatment agent of the base material is due to the orientation of the Rf group in the treatment film, and the Rf group is further oriented. It is said that it is necessary that the melting point of the microcrystal derived from the Rf group (8 or more carbon atoms) exists, and therefore, it contains a perfluoroalkyl group having a perfluoroalkyl group having 8 or more carbon atoms (meth). It is stated that acrylates have been used.
• telomer compounds currently used as raw materials for surface modifiers such as water and oil repellents
• compounds having a perfluoroalkyl group having 8 or more carbon atoms may become PFCA in the environment.
• a compound having a perfluoroalkyl group having 6 or less carbon atoms is said to have low bioaccumulation, but a compound having a perfluoroalkyl group having 6 or less carbon atoms is a flexible water-repellent oil-repellent agent. It is said that it is difficult to obtain the performance required for such products.
• the conventional water- and oil-repellent coating agent has no flexibility in the film formed from it, and cracks occur due to a slight impact or pressure, so that the usage is limited.
• An object of the present invention is to provide a flexible water-repellent oil-repellent agent in which a film formed from a coating agent adheres to and follows the deformation of rubber or resin and exhibits water-repellent and oil-repellent properties.
• Perfluoropolyether alcohol (meth) acrylic acid derivative represented by (where R 1 is a hydrogen atom or a methyl group and n is an integer of 1 to 20) and the general formula CH 2 CR 1 COOR 2 [II] (Here, R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group or an aralkyl group), and the glass transition temperature Tg is 51 to 120 ° C. It is achieved by a flexible water-repellent oil-repellent agent containing a copolymer of a (meth) acrylic acid ester as an active ingredient.
• (meth) acrylic acid means acrylic acid or methacrylic acid.
• the film formed from the coating agent adheres to and follows the deformation of rubber or resin, exhibits water-repellent oil-repellent property, and is tack-free even in a tack property test.
• the fluorine-containing copolymer used in the present invention has many ether bonds that lower the glass transition temperature Tg during copolymer formation, it is possible to form a flexible film and its surface energy is very small. It is possible to sufficiently exhibit the performance required for a water-repellent oil-repellent agent such as water-repellent oil-repellent property, mold release property, and antifouling property.
• the water- and oil-repellent agent of the present invention contains a copolymer of a perfluoropolyether alcohol (meth) acrylic acid derivative represented by the following formula [I] and a (meth) acrylic acid ester represented by the following [II] as an active ingredient. do.
• R 1 Hydrogen atom or methyl group, preferably methyl group n: an integer of 1 to 20, preferably an integer of 1 to 4
• CH 2 CR 1 COOR 2
• R 1 Hydrogen atom or methyl group, preferably methyl group
• R 2 Alkyl group, alkoxyalkyl group, cycloalkyl group, Aryl group, aralkyl group, preferably alkyl group
• the perfluoropolyether alcohol (meth) acrylic acid derivative [I] is a known compound and is described in, for example, Patent Document 1.
• perfluoropolyether alcohol derived from hexafluoropropylene oxide C 3 F 7 O [CF (CF 3 ) CF 2 O] n CF (CF 3 ) CH 2 OH is esterified with (meth) acrylic acid halide.
• the following compounds produced by reaction are exemplified.
• the (meth) acrylic acid ester [II] must have a glass transition temperature Tg (measured according to JIS K7121 corresponding to ISO 3146) of 51 to 120 ° C, preferably 65 to 105 ° C, for example, methacrylic acid.
• Tg glass transition temperature
• Methyl (Tg: 105 ° C), ethyl methacrylate (Tg: 65 ° C) and the like are used.
• (meth) acrylic acid esters [II] are used in a proportion of about 5 to 30% by weight, preferably about 5 to 10% by weight in the copolymer. If the copolymerization ratio of (meth) acrylic acid ester [II] is smaller than this, the softening effect is not exhibited, while if it is used in a larger ratio than this, the water and oil repellency becomes inferior.
• the copolymerization reaction is also carried out by an emulsion polymerization method or a turbidity polymerization method, but is preferably carried out by a solution polymerization method.
• the reaction solvent of the solution polymerization method is not particularly limited as long as it is a solvent in which the fluorine-containing copolymer dissolves, but an organic solvent having a fluorine atom is preferable.
• the polymerization reaction is carried out in a fluorine-containing organic solvent such as hydrofluoroether.
• hydrofluorocarbons and hydrofluoro ethers are also used.
• Hydrofluorocarbon CF 3 (CF 2 ) 2 CHF 2 , CF 3 (CF 2 ) 2 CH 2 F, CF 3 CF 2 CH 2 CF 3 , F 2 CH (CF 2 ) 2 CHF 2 , F 2 CHCH 2 CF 2 CF 3 , CF 3 CHFCH 2 CF 3 , CF 3 CH 2 CF 2 CHF 2 , F 2 CHCHFCF 2 CHF 2 , CF 3 CHFCF 2 CH 3 , F 2 CH (CHF) 2 CHF 2 , CF 3 CH 2 CF 2 CH 3 , F 2 CHCH 2 CF 2 CH 3 , F 2 CH (CF 2 ) 3 CF 3 , F 2 CHCH 2 CF 2 CH 3 , F 2 CH (CF 2 ) 3 CF 3 , CF 3 (CF 2 ) 2 CHFCF 3 , F 2 CH (CF 2 ) 3 CHF 2 , CF 3 (CF 2 ) 2 CHFCF 3 , F 2 CH (CF 2 ) 3 CHF 2
• Hydrofluoroether CF 3 CF 2 CF 2 OCH 3 , (CF 3 ) 2 CFOCH 3 , CF 3 (CF 2 ) 2 OCH 2 CH 3 , CF 3 (CF 2 ) 3 OCH 3 , (CF 3 ) 2 CFCF 2 OCH 3 , C (CF 3 ) 3 OCH 3 , CF 3 (CF 2 ) 3 OCH 2 CH 3 , (CF 3 ) 2 CFCF 2 OCH 2 CH 3 , (CF 3 ) 3 COCH 2 CH 3 , CF 3 CF ( OCH 3 ) CF (CF 3 ) 2 , CF 3 CF (OCH 2 CH 3 ) CF (CF 3 ) 2 , C 5 F 11 OCH 2 CH 3 , CF 3 (CF 2 ) 2 CF (OCH 2 CH 3 ) CF (CF 3 ) 2 , CH 3 O (CF 2 ) 4 OCH 3 , CH 3 O (CF 2 ) 2 OCH 2 CH 3 , C 3 H 7 OCF
• the solubility of the perfluoropolyether alcohol (meth) acrylic acid ester in a fluorine-containing organic solvent is not good, it is preferable to mix it with an alcohol.
• the alcohol is not particularly limited, but the obtained fluorine-containing copolymer is soluble, has good compatibility with a fluorine-containing organic solvent, and is compatible with a perfluoropolyether alcohol (meth) acrylic acid derivative. Is preferable.
• isopropyl alcohol or the like is used as such alcohol.
• aliphatic hydrocarbons Similar to alcohol, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, esters, ketones, etc. can also be used.
• Aliphatic hydrocarbons n-pentane, 2-methylbutane, n-hexane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, n-octane, 2,2,4- Trimethylpentane, n-nonane, 2,2,3-trimethylhexane, n-decane, n-undecane, n-dodecane, 2,2,4,6,6-pentamethylheptane, n-tridecane, n-tetradecane, Alicyclic hydrocarbons such as n-hexadecan: cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.
• Aromatic hydrocarbons benzene, toluene, xylene, 1,4-bis (trifluoromethyl) benzene, 1,3-bis ( Trifluoromethyl) benzene, etc.
• Esters methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, pentyl lactate, etc.
• Ketones acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methylisobutyl Ketone, etc.
• the weight ratio of each charged monomer is approximately the copolymerization composition weight ratio of the produced copolymer.
• ethylenically unsaturated monomers such as styrene, ⁇ -methylstyrene, vinyltoluene, vinylnaphthalene, (meth) acrylonitrile, acrylic acid amide, vinyl acetate, etc.
• Ethylene, propylene, piperylene, butadiene, isoprene, pentadiene and the like can be copolymerized at a ratio that does not impair the flexibility of the copolymer of the present invention.
• a polyfunctional (meth) acrylate or oligomer having a glycol residue in the side chain for example, ethylene glycol, propylene glycol, 1,4- Di (meth) acrylate of alkylene glycol such as butanediol, 1,6-hexanediol, 1,9-nonanediol, di (meth) acrylate such as neopentyl glycol, tetraethylene glycol, tripropylene glycol, polypropylene glycol, bisphenol A.
• Ethylene oxide adduct diacrylate, dimethylol tricyclodecane diacrylate, glycerin methacrylate acrylate, 3-acryloyloxyglycerin monomethacrylate and the like can be further copolymerized and used.
• the initiator used in a ratio of about 0.1 to 4% by weight, preferably about 1 to 2% by weight, based on the total amount of the comonomono, diacyl peroxide, peroxycarbonate, peroxyester or the like is used, and concretely These include isobutyryl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, bis (heptafluorobutyryl) peroxide, pentafluorobutyroyl peroxide, and bis (4-thbutylcyclohexyl) peroxydi.
• Organic peroxides such as carbonate, di-n-propylperoxydicarbonate, and diisopropylperoxydicarbonate are used, and azo compounds, inorganic peroxides, or redox systems thereof are also used depending on the polymerization reaction.
• the polymerization initiator may be added and used again in the middle of the polymerization reaction.
• a chain transfer agent can be used as needed to adjust the molecular weight.
• the chain transfer agent include dimethyl ether, methyl tertiary butyl ether, alkanes having 1 to 6 carbon atoms, methanol, ethanol, and 2 -Propanol, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, methane, ethyl acetate, ethyl malonate, acetone and the like can be mentioned.
• the copolymerization reaction is carried out using these reaction solvents, reaction initiators, etc., preferably at a reaction temperature of about 60 to 80 ° C. for about 10 to 24 hours. After completion of the reaction, a copolymer solution having a solid content concentration of about 5 to 40% by weight is obtained, and a fluorine-containing copolymer is obtained by removing the solvent from this reaction mixture.
• the perfluoropolyether alcohol (meth) acrylic acid derivative [I] used in the copolymerization reaction was confirmed to be almost completely copolymerized as a result of gas chromatography analysis of the unreacted residual comonomer. Will be done.
• the method for producing a copolymer of a polyfluoroalkyl alcohol (meth) acrylic acid derivative is not limited to such a solution polymerization method, and is turbidity containing, for example, water as a dispersion medium and a nonionic surfactant and / or a cationic surfactant.
• a polymerization method, an emulsion polymerization method and the like are also used.
• the copolymer of the polyfluoroalkyl alcohol (meth) acrylic acid derivative thus obtained is separated by a method of evaporating to dryness, a method of adding a flocculant such as an inorganic salt to coagulate, and washing with a solvent or the like. Purify by the method of The weight average molecular weight Mw of the obtained copolymer is shown by high performance liquid chromatography, and its value is about 2,000 to 2,000,000.
• the polymer solution obtained by the solution polymerization method is further used for a fluorine-containing organic solvent such as 1,4-bis (trifluoromethyl) benzene and 1,3-bis (trifluoromethyl) benzene, preferably for a polymerization reaction. It is used as a coating agent after being diluted with the same fluorine-containing organic solvent as the above to have a solid content concentration of about 0.01 to 30% by weight, preferably about 0.05 to 15% by weight.
• a turbid polymerization method, etc. it can be used as it is or after diluting the solid content concentration with water to about 0.1 to 10% by weight as an aqueous dispersion.
• an aqueous dispersion is prepared by adding a flocculant to the polymerization reaction solution to coagulate the polymer, washing the polymer with water or an organic solvent, and dissolving the separated copolymer in water or in a fluorine-containing organic solvent.
• a flocculant to the polymerization reaction solution to coagulate the polymer
• washing the polymer with water or an organic solvent and dissolving the separated copolymer in water or in a fluorine-containing organic solvent.
• an organic solvent solution Coating agents can also be prepared.
• a liquid containing 20% by weight or less of a surfactant and a water-soluble organic solvent is preferably used as the aqueous dispersion.
• additives include a cross-linking agent such as melamine resin, urea resin and blocked isocyanate, a polymer extender and silicone.
• Additives necessary for applications such as resins, other water repellents such as oils and waxes, insect repellents, antistatic agents, dye stabilizers, wrinkle repellents, and stain blockers can be added.
• the copolymer solution thus obtained is effectively applied as a water and oil repellent to various rubber products, elastic resin products and the like.
• coating, dipping, spraying, padding, roll coating or a combination method thereof is generally used.
• the material to be treated is padded in this pad bath, and if necessary, the excess liquid is removed by a drawing roll and dried so that the amount of the adhered fluorine-containing copolymer with respect to the material to be treated is about 0.01 to 10% by weight. Attach to. After that, although it depends on the type of the material to be treated, it is generally dried at a temperature of about 100 to 200 ° C. for about 1 minute to about 2 hours, and the water-repellent and oil-repellent treatment is completed.
• Example 3 In Example 2, 0.73 g of ethyl methacrylate (Tg: 65 ° C.) was used instead of methyl methacrylate. The amount of solvent was changed to 18.35 g and the amount of polymerization initiator was changed to 44.0 mg, respectively, and a polymerization reaction solution having a solid content concentration of 31.3% by weight was obtained.
• Tg 65 ° C.
• Example 4 In Example 2, the amount of PO-3-MAC was changed to 8.26 g, and 54.8 mg of 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate [Showa Denko products Karenz MOI-BP] was a crosslinkable monomer. Was used as. The amount of the solvent was changed to 18.26 g and the amount of the polymerization initiator was changed to 44.7 mg, respectively, and a polymerization reaction solution having a solid content concentration of 31.9% by weight was obtained.
• Example 2 28.1 mg of 2-hydroxyethyl acrylate [2HEA] was additionally used as a crosslinkable monomer.
• the amount of solvent was changed to 18.21 g and the amount of polymerization initiator was changed to 44.6 mg, but since 2HEA has low compatibility with the solvent Novec 7300, the product becomes cloudy and solidified, and various characteristics can be measured. There wasn't.
• Example 4 Comparative Example 4 In Example 1, 0.82 g of n-butyl acrylate (Tg: -49 ° C.) was used instead of methyl methacrylate. Although the amount of solvent was changed to 18.09 g, the product was a liquid product having no solid content, and various properties could not be measured.
• Tg -49 ° C.
• Example 2 Comparative Example 5 In Example 2, 0.91 g of n-butyl methacrylate (Tg: 20 ° C.) was used instead of methyl methacrylate. The amount of solvent was changed to 17.91 g, and a polymerization reaction solution having a solid content concentration of 27.6% by weight was obtained.
• Tg 20 ° C.

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