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WO2010101091A1 - Agent de modification de surface contenant un polymère fluoré comme composant actif - Google Patents

Agent de modification de surface contenant un polymère fluoré comme composant actif Download PDF

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Publication number
WO2010101091A1
WO2010101091A1 PCT/JP2010/053113 JP2010053113W WO2010101091A1 WO 2010101091 A1 WO2010101091 A1 WO 2010101091A1 JP 2010053113 W JP2010053113 W JP 2010053113W WO 2010101091 A1 WO2010101091 A1 WO 2010101091A1
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integer
surface modifier
weight
group
reaction
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Japanese (ja)
Inventor
智 栗原
清一郎 村田
勝之 佐藤
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Unimatec Co Ltd
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Unimatec Co Ltd
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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
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • 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
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon 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
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to a surface modifier having a fluoropolymer as an active ingredient. More specifically, a fluoropolymer that is a homopolymer or copolymer of a (meth) acrylic acid derivative containing a perfluoroalkyl group having 6 or less carbon atoms, which is said to have low bioaccumulation, is used as an active ingredient.
  • the present invention relates to a surface modifier.
  • perfluoroalkyl alcohol which is an acrylated precursor is widely used as a surfactant and the like.
  • Patent Document 2 the expression of water and oil repellency by the perfluoroalkyl group [Rf] -containing (meth) acrylate in the surface treatment agent of the base material is caused by the orientation of the Rf group in the treated film, and the Rf group is further oriented.
  • the melting point of microcrystals derived from the Rf group carbon number of 8 or more
  • a perfluoroalkyl group containing a perfluoroalkyl group having a carbon number of 8 or more (meta) 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 C8 or more perfluoroalkyl group may become PFCA in the environment.
  • compounds having a perfluoroalkyl group having 6 or less carbon atoms it is said that the bioaccumulation is low, but in compounds having a perfluoroalkyl group having 6 or less carbon atoms, surface modifiers, etc. It is said that it is difficult to obtain the performance required for the product.
  • An object of the present invention is a fluoropolymer comprising a homopolymer of a fluoroalkyl alcohol (meth) acrylic acid derivative having a perfluoroalkyl group having 6 or less carbon atoms, which is said to have low bioaccumulation, or a copolymer thereof. It is in providing the surface modifier which uses as an active ingredient.
  • n is preferably an integer of 2 to 4
  • a is an integer of 1 to 2
  • b is 1 to 3 from the viewpoints of stability of the polymerization solution during polymerization, solubility, and polymerization rate.
  • C is an integer of 1 to 2.
  • the fluoropolymer which is a homopolymer of a fluoroalkyl alcohol (meth) acrylic acid derivative or a copolymer thereof according to the present invention is merely composed of a perfluoroalkyl group having 6 or less carbon atoms with low bioaccumulation. Rather, the CH 2 CF 2 group derived from vinylidene fluoride in the molecule easily de-HFs to form a double bond, which is susceptible to decomposition by ozonolysis, so it is less likely to inhibit the environment, In addition, since it has surface modification performance equivalent to that of conventional fluoropolymers, it can be suitably used as an active ingredient of surface modifiers such as water and oil repellents and oil barriers.
  • the fluoroalkyl alcohol (meth) acrylic acid derivative used as the monomer for the fluoropolymer has the general formula C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OH Is produced by an esterification reaction with acrylic acid or methacrylic acid.
  • (meth) acrylic acid indicates acrylic acid or methacrylic acid (hereinafter the same).
  • This fluoroalkyl alcohol is produced from the corresponding fluoroalkyl iodide.
  • Fluoroalkyl iodide as starting material for fluoroalkyl alcohol synthesis C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c I Is the general formula C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b I (I) It is manufactured by carrying out addition reaction of ethylene to the terminal iodination compound represented by these. The addition reaction of ethylene is carried out by adding pressurized ethylene to the above compound [I] in the presence of a peroxide initiator. The number of addition depends on the reaction conditions, but it is 1 or more, preferably 1 to 3, more preferably 1.
  • this addition reaction is related to the decomposition temperature of the initiator used, it is generally performed at a reaction temperature of about 80 to 120 ° C., and when a peroxide initiator that decomposes at a low temperature is used, 80 ° C. The following reactions are possible.
  • Peroxide initiators include tertiary butyl peroxide, di (tertiary butyl cyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, diisopropyl Secondary butyl peroxydicarbonate and the like can be mentioned, and they are used in a proportion of about 1 to 5 mol% based on the above compound [I] from the viewpoint of the progress and controllability of the reaction.
  • the compound [I] is synthesized through the following series of steps.
  • General formula C n F 2n + 1 I (n: 1 to 6) Is reacted with vinylidene fluoride in the presence of a peroxide initiator (amount used in an amount of about 0.1 to 0.5 mol% based on the starting compound) as described above, to give a general formula C n F 2n + 1 (CH 2 CF 2 ) a I (II)
  • the terminal iodinated compound represented by the general formula [I] is obtained by reacting the compound represented by the general formula [II] with tetrafluoroethylene in the presence of a peroxide initiator. .
  • the peroxide initiator used in this reaction the organic peroxide initiator as described above is used in the same ratio as in the vinylidene fluoride addition reaction.
  • reaction temperature of vinylidene fluoride and tetrafluoroethylene addition reaction also depends on the decomposition temperature of the initiator used, but by using a peroxide initiator that decomposes at low temperatures, Reaction is possible. Reaction, C n F 2n + 1 put I or the compound [II] into the autoclave, about 10 ⁇ 60 ° C.
  • n F 2n + 1 When a peroxide initiator dissolved in I or compound [II] is added and the internal temperature reaches 55 ° C., for example, vinylidene fluoride or tetrafluoroethylene is added while maintaining a pressure of about 0.1 to 1.0 MPa, After the desired amount is dispensed, for example, aging is performed at a temperature of about 55 to 80 ° C. for about 1 hour.
  • the number a or b of vinylidene fluoride or tetrafluoroethylene skeleton added by the reaction depends on the amount added. Generally, it is formed as a mixture of various a and b values.
  • Specific compounds [I] to which ethylene is added include the following compounds.
  • This compound is a mixture of oligomers having various a and b values, and oligomers having specific a and b values can be isolated by distilling the mixture.
  • prescribed a value and b value can be used again for the oligomer number increase reaction with vinylidene fluoride or tetrafluoroethylene, isolating it or with a mixture.
  • Fluoroalkyl alcohols are obtained by first reacting a fluoroalkyl iodide with N-methylformamide HCONH (CH 3 ) to form a mixture of the fluoroalkyl alcohol and its formate, and then hydrolyzing it in the presence of an acid catalyst. It is manufactured by. In this reaction, in order to prevent the CH 2 CF 2 derived from vinylidene fluoride bonded in the fluoroalkyl iodide from causing deHF and reducing the yield, preferably 5 to 10 times the molar amount It is preferable to use about N-methylformamide and to use an aqueous solution of p-toluenesulfonic acid as the acid catalyst. The reaction with N-methylformamide is carried out at a temperature of about 140 to 160 ° C. for about 4 to 5 hours, and the subsequent hydrolysis reaction is carried out at a temperature of about 70 to 90 ° C. for about 7 to 8 hours. .
  • N-methylformamide HCONH CH 3
  • the obtained fluoroalkyl alcohol can be esterified with acrylic acid or methacrylic acid.
  • an aromatic hydrocarbon solvent such as toluene and benzene
  • a catalyst such as p-toluenesulfonic acid and hydroquinone as a polymerization inhibitor are added to fluoroalkyl alcohol and heated to about 90 to 100 ° C.
  • About 1-2 mol of acrylic acid or methacrylic acid is added thereto, and heated at about 110-120 ° C. for about 2-5 hours for dehydration reaction to carry out an esterification reaction.
  • the fluoroalkyl alcohol (meth) acrylic acid derivative is polymerized by itself, but can be copolymerized with a fluorine atom-free polymerizable monomer and / or another fluorine-containing polymerizable monomer.
  • R 1 (CH 2 ) p OCOCR CH 2 R: hydrogen atom or methyl group
  • R 1 hydrogen atom, alkyl group, alkoxyalkyl group, cycloalkyl group, aryl group or aralkyl group
  • p (meth) acrylic acid ester represented by an integer of 1 to 20, specifically Is methyl, ethyl, propyl, isopropyl, n-butyl, n-hexyl, 2-ethylhexyl, n-octyl, lauryl, stearyl and other alkyl groups, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl , An alkoxyalkyl group such as 3-ethoxypropyl, a cycloalkyl group such as cyclohexyl, an aryl group such as pheny
  • Monoalkyl esters or dialkyl esters such as benzene, monoethyl, diethyl, monopropyl, dipropyl, monobutyl, dibutyl, mono-2-ethylhexyl, di2-ethylhexyl, monooctyl, dioctyl, vinyl esters such as vinyl acetate, vinyl caprylate, etc. Used.
  • it is a long-chain alkyl group having 8 or more carbon atoms, more preferably 8 to 20 carbon atoms, for example, an alkyl (meth) acrylate having an alkyl group such as 2-ethylhexyl, n-octyl, lauryl or stearyl, or a cycloalkyl group such as cyclohexyl.
  • an alkyl (meth) acrylate having an alkyl group such as 2-ethylhexyl, n-octyl, lauryl or stearyl, or a cycloalkyl group such as cyclohexyl.
  • Acrylates esterified with aralkyl groups such as benzyl, particularly preferably stearyl (meth) acrylate and benzyl (meth) acrylate are preferred in terms of the balance of coating properties, water repellency and oil repellency of the treated substrate. Used.
  • copolymer other copolymerizable monomers other than the fluorine atom-free polymerizable monomer can be copolymerized within a range in which the characteristics are not impaired.
  • copolymerizable monomers include ethylene, styrene, vinylidene chloride, vinyl chloride, vinyl acetate, vinyl fluoride, vinylidene fluoride, vinyl toluene, ⁇ -methyl styrene, p-methyl styrene, vinyl naphthalene, acrylonitrile, Methacrylonitrile, isoprene, pentadiene, butadiene, chloroprene, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, aziridinylethyl (meth) acrylate, aziridinyl (meth) acrylate, polysiloxane-containing (meth) acrylate, polyoxy Alkylene (meth)
  • a polyfunctional monomer or oligomer can be copolymerized at a ratio of 30% by weight or less in the copolymer.
  • Such polyfunctional monomers or oligomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly Oxyalkylene di (meth) acrylate, alkylene di (meth) acrylate, bisphenol A / ethylene oxide adduct diacrylate, dimethylol tricyclodecane
  • Y (CH 2 ) q OCH 2 NHOCCR CH 2 R: hydrogen atom or methyl group
  • Y hydrogen atom or hydroxyl group
  • q a crosslinkable group-containing monomer represented by an integer of 0 to 4, such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl Add acrylamide, N, N-dimethyl (meth) acrylamide, N-butoxymethyl acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, glycidyl (meth) acrylate, etc., about 10% by weight or less in the copolymer
  • the copolymerization can preferably be carried out at a ratio of about 0.5 to 7% by weight.
  • the fluoroalkyl alcohol (meth) acrylic acid derivative monomer in the copolymer is about 5% by weight or more, preferably about 50 to 90% by weight. It is preferable to carry out the copolymerization at such a ratio as to occupy the water and oil repellency. Of course, water and oil repellency is exhibited even in a homopolymer in which this monomer accounts for 100% by weight, but in terms of cost, a copolymer with another comonomer is advantageous.
  • the polyfluoroalkyl group-containing (meth) acrylate monomer exhibiting water / oil repellency itself is copolymerized in an amount of 30 to 90% by weight, preferably 50 to 70% by weight, in the copolymer, water and oil repellency and It is preferable from the viewpoint of cost.
  • the solvent to be used is not particularly limited, but from the viewpoint of ease of handling, a halogen group-containing solvent such as an ester solvent, a hydrocarbon solvent, chlorofluorocarbon, perfluorocarbon, etc., preferably 1,4-bis (Trifluoromethyl) benzene, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, 1,1 , 1,2,3,4,4,5,5,5-Decafluoropentane, perfluorohexane and other fluorine-containing organic solvents, aliphatic and alicyclic hydrocarbons Azo compounds such as azobisisobutyronitrile or bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-n-propylperoxydicarbonate in an ester solvent such as ethyl acetate , Diiso An
  • the method for producing a homopolymer or copolymer of a fluoroalkyl alcohol (meth) acrylic acid derivative is not limited to such a solution polymerization method, and includes, for example, water as a dispersion medium and a nonionic surfactant and / or a cationic surfactant. Suspension polymerization, emulsion polymerization, and the like are also used.
  • the homopolymer or copolymer of the fluoroalkyl 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 agglomerate, and the like. It refine
  • the weight average molecular weight Mw of the obtained homopolymer or copolymer is shown by a high performance liquid chromatography method, and its value is about 2,000 to 20,000,000.
  • the polymer solution obtained by the solution polymerization method further includes ester solvents such as ethyl acetate, butyl acetate and amyl acetate, glycol solvents such as ethylene glycol and propylene glycol, ketone solvents such as acetone and ethyl methyl ketone, n -Solid content concentration of about 0.01 to 30% by weight, preferably about 0.05 by non-fluorinated organic solvent mainly composed of aliphatic, alicyclic or aromatic hydrocarbon solvents such as hexane, cyclohexane, paraffin and alkylbenzene Diluted to ⁇ 5% by weight and used as a surface modifier.
  • ester solvents such as ethyl acetate, butyl acetate and amyl acetate
  • glycol solvents such as ethylene glycol and propylene glycol
  • ketone solvents such as acetone and ethyl methyl ketone
  • the non-fluorinated organic solvent By adding a flocculant to the polymerization reaction solution to aggregate the polymer, washing with an organic solvent and separating the separated homopolymer or copolymer in the non-fluorinated organic solvent, the non-fluorinated organic solvent It can also be prepared as a solution.
  • Such an organic solvent solution can be used as a surface modifier such as a water / oil repellent or an oil barrier.
  • a polymer solution comprising a non-fluorinated organic solvent solution of a fluoroalkyl alcohol (meth) acrylic acid derivative homopolymer or copolymer
  • further additives such as melamine resin, urea resin, blocked isocyanate, etc.
  • Other water repellents such as crosslinking agents, polymer extenders, silicone resins or oils, waxes, insecticides, antistatic agents, dye stabilizers, antifungal agents, additives necessary for surface modifiers such as stain blockers Can be added.
  • the surface modifier thus obtained is a water / oil / oil repellent or a watch, a motor, a fabric product made of metal, paper, film, fiber, cloth, woven fabric, carpet or filament, fiber, thread, etc.
  • a surface modifier such as an oil barrier that prevents the lubricant from seeping out from the sliding surface to the periphery of sliding parts of precision machines such as lenses of single-lens reflex cameras or parts close to the sliding parts
  • coating, dipping, spraying, padding, roll coating, or a combination thereof is generally used. For example, by using a solid content concentration of the bath of about 0.1 to 10% by weight, it can be used as a pad bath. Is done.
  • the material to be treated is padded in this pad bath, then excess liquid is removed with a squeeze roll and dried, and the polymer is attached to the material to be treated so that the amount of the polymer is about 0.01 to 10% by weight. Thereafter, depending on the type of material to be treated, drying is generally performed at a temperature of about 100 to 200 ° C. for about 1 minute to about 2 hours, and the water and oil repellent treatment is completed.
  • Example 1 To a 1200 ml autoclave equipped with a stirrer and a thermometer, CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I (99.9GC%) 529 g (0.86 mol) and 5 g of di-tert-butyl peroxide were charged, and the autoclave was deaerated with a vacuum pump. When the internal temperature was heated to 80 ° C., ethylene was sequentially introduced to adjust the internal pressure to 0.5 MPa. When the internal pressure dropped to 0.2 MPa, ethylene was introduced again to 0.5 MPa, and this was repeated.
  • the reaction product was distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 121 to 163 ° C, and a tower top temperature of 76 to 77 ° C, and purified reaction product (95.3GC%) 66.9g (distillation yield 94.2%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR. CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) OH
  • reaction mixture was cooled to recover 82 g of the reaction solution, and 63.9 g of the residue from which toluene was removed with an evaporator was washed with tap water, and a reaction product (89.3 GC%) that was a colorless and transparent liquid at room temperature was used as the lower layer 60.8 g (yield 86.4%) was obtained.
  • the reaction product was distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 125 to 155 ° C, and a tower top temperature of 84 to 86 ° C, and purified reaction product (99.4GC%) 42.2g (distillation yield 77.2%) Got.
  • the weight average molecular weight Mw of the fluoropolymer isolated by removing the solvent from the used polymer solution in an oven at 120 ° C. was 34,000.
  • the weight average molecular weight Mw was measured by GPC measurement using Shodex GPC KD806 + KD-802 at a temperature of 40 ° C and an elution rate of 10 mM ⁇ ⁇ THF as an eluent at 1 ml / min.
  • the total and analysis were performed by Labchat180 (polystyrene conversion) manufactured by SIC.
  • the obtained polymer solution was mixed with a petroleum solvent (mineral terpene) and C9 to C12 paraffin: C 9 to C 10 alkylbenzene (weight ratio 70:30) to a solid content concentration of 0.5% by weight. Diluted to prepare a surface modifier.
  • a petroleum solvent mineral terpene
  • C9 to C12 paraffin C 9 to C 10 alkylbenzene (weight ratio 70:30)
  • Example 2 In Example 1 (4), an aliphatic / alicyclic hydrocarbon compound (naphtha): nonane mixed solvent (weight ratio 90:10) as a polymerization solvent for obtaining the final reaction product (Yamaichi Chemical Products MC -D40) was used to prepare the polymer solution.
  • the polymer solution thus obtained had a solid content concentration of 31.3% by weight, and the fluorine-containing polymer had a weight average molecular weight Mw of 35,000.
  • the surface modifier was prepared.
  • Example 3 In Example 1 (4), a polymer solution was prepared using ethyl acetate as a polymerization solvent for obtaining a final reaction product.
  • the polymer solution thus obtained had a solid content concentration of 30.9% by weight, and the weight average molecular weight Mw of the fluoropolymer was 33,000.
  • the surface modifier was prepared.
  • Example 4 In Example 1 (1), CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 3 I (99.7GC%) as a fluoroalkyl iodide Using 712 g (1.17 mol), changing the amount of tertiary butyl peroxide to 7 g, carrying out a reaction introducing 49 g (1.7 mol) of ethylene, CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) I (98.3GC%) 754 g (99.6% yield) was obtained.
  • the reaction product was distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 126 to 165 ° C, and a tower top temperature of 75 to 78 ° C, and purified reaction product (95.9GC%) 45.2g (distillation yield 84.2%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR. CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) OH
  • reaction mixture was cooled to recover 75 g of the reaction solution, and 43.0 g of the residue from which toluene was removed with an evaporator was washed with tap water, and the reaction product (87.6 GC%), which was a colorless and transparent liquid at room temperature, was used as the lower layer. 45.3 g (yield 88.8%) was obtained.
  • the reaction product is distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 125 to 160 ° C, and a tower top temperature of 85 to 87 ° C, and 18.9 g of a purified reaction product (99.5GC%) (distillation yield 47.4%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
  • CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) OCOCH CH 2
  • Example 5 (1) In Example 1, (1), CF 3 (CF 2 ) 3 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) I (99.7GC%) as a fluoroalkyl iodide Using 670 g (1.17 mol), changing the amount of tertiary butyl peroxide to 7 g, carrying out a reaction to introduce 49 g (1.7 mol) of ethylene, CF 3 (CF 2 ) 3 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) I (98.5GC%) 706 g (99.0% yield) was obtained.
  • the reaction mixture was washed with 30 ml of water, and the lower layer (82 g) was mixed with 83 g of a 15 wt% p-toluenesulfonic acid aqueous solution and stirred at 80 ° C. for 8 hours. After allowing the reaction mixture to stand, 65 g (yield: 55.0%) of a reaction product (73.8 GC%) as a white solid was obtained as the lower layer.
  • the reaction product was distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 126 to 167 ° C, and a tower top temperature of 75 to 76 ° C, and 44.1 g of purified reaction product (95.2 GC%) (distillation yield 87.5%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR. CF 3 (CF 2 ) 3 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) OH
  • reaction mixture was cooled to recover 69 g of the reaction solution, and 43.1 g of the residue from which toluene was removed with an evaporator was washed with tap water, and a reaction product (85.9 GC%) that was a colorless and transparent liquid at room temperature was used as the lower layer. 44.5 g (yield 81.7%) was obtained.
  • the reaction product is distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 125 to 158 ° C, and a tower top temperature of 85 to 86 ° C, and 15.7 g of purified reaction product (99.0 GC%) (distillation yield 40.7%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
  • Example 6 (1) In (1) of Example 1, CF 3 (CF 2 ) (CH 2 CF 2 ) 2 (CF 2 CF 2 ) 2 I (99.8GC%) as a fluoroalkyl iodide Using 670 g (1.17 mol), changing the amount of tertiary butyl peroxide to 7 g, carrying out a reaction to introduce 49 g (1.7 mol) of ethylene, CF 3 (CF 2 ) (CH 2 CF 2 ) 2 (CF 2 CF 2 ) 2 (CH 2 CH 2 ) I (98.4GC%) 711 g (99.5% yield) was obtained.
  • the reaction product is distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 123 to 163 ° C, and a tower top temperature of 72 to 74 ° C. 44.6g of purified reaction product (94.8GC%) (distillation yield 84.7%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR. CF 3 (CF 2 ) (CH 2 CF 2 ) 2 (CF 2 CF 2 ) 2 (CH 2 CH 2 ) OH
  • the reaction mixture was cooled to recover 71 g of the reaction solution, and 45.1 g of the residue from which toluene was removed with an evaporator was washed with tap water, and the reaction product (86.2 GC%), which was a colorless and transparent liquid at room temperature, was used as the lower layer. 43.8 g (yield 81.0%) was obtained.
  • the reaction product is distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 122 to 160 ° C., and a tower top temperature of 86 to 88 ° C., and 15.6 g of a purified reaction product (99.2 GC%) (distillation yield 41.0%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
  • CF 3 (CF 2 ) (CH 2 CF 2 ) 2 (CF 2 CF 2 ) 2 (CH 2 CH 2 ) OCOCH CH 2
  • Example 7 (1) In Example 1, (1), CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) I (99.8GC%) as a fluoroalkyl iodide Using 603 g (1.17 mol), changing the amount of tertiary butyl peroxide to 7 g, carrying out a reaction to introduce ethylene 49 g (1.7 mol), CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) I (98.3GC%) 635 g (98.8% yield) was obtained.
  • the reaction product was distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 100 to 144 ° C., and a tower top temperature of 58 to 59 ° C., and 43.7 g of purified reaction product (95.4GC%) (distillation yield 88.2%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR. CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) OH
  • reaction mixture was cooled to recover 72 g of the reaction solution, and 44.5 g of the residue from which toluene was removed with an evaporator was washed with tap water, and a reaction product (86.3 GC%) that was a colorless and transparent liquid at room temperature was used as the lower layer 40.9 g (yield 82.6%) was obtained.
  • the reaction product was distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 103 to 143 ° C, and a tower top temperature of 60 to 61 ° C, and purified reaction product (99.2GC%) 15.7g (distillation yield 44.1%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
  • CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) OCOC (CH 3 ) CH 2
  • Example 8 (1) In Example 1 (1), CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I (99.6 GC%) as a fluoroalkyl iodide Using 594 g (1.17 mol), changing the amount of tertiary butyl peroxide to 7 g, carrying out a reaction introducing 49 g (1.7 mol) of ethylene, CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) I (98.9GC%) 627 g (98.9% yield) was obtained.
  • the reaction product was distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 100 to 157 ° C, and an overhead temperature of 59 to 61 ° C, and 42.6 g of purified reaction product (94.9GC%) (distillation yield 85.3%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR. CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) OH
  • reaction mixture was cooled to recover 74 g of the reaction solution, and 43.9 g of the residue from which toluene was removed with an evaporator was washed with tap water, and the reaction product (86.2 GC%), which was a colorless and transparent liquid at room temperature, was used as the lower layer. 40.8 g (yield 85.4%) was obtained.
  • the reaction product was distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 114 to 155 ° C, and a tower top temperature of 66 to 69 ° C, and purified reaction product (99.1GC%) 13.8g (distillation yield 38.9%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
  • CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) OCOC (CH 3 ) CH 2
  • Example 9 In Example 2, a polymer solution was prepared using 15 g (0.05 mol) of stearyl acrylate instead of stearyl methacrylate. The polymer solution thus obtained had a solid concentration of 31.0% by weight, and the weight average molecular weight Mw of the fluoropolymer was 35,000. Next, using the obtained polymer solution, a solid content concentration of 0.5% by weight with a mixed solvent composed of petroleum solvent (mineral terpene), C9 to C12 paraffin: C 9 to C 10 alkylbenzene (weight ratio 70:30) The surface modifier was prepared.
  • a mixed solvent composed of petroleum solvent (mineral terpene), C9 to C12 paraffin: C 9 to C 10 alkylbenzene (weight ratio 70:30) The surface modifier was prepared.
  • Example 10 The polymer solution obtained in Example 2 was diluted with ethyl acetate to a solid content concentration of 0.5% by weight to prepare a surface modifier.
  • Example 11 The polymer solution obtained in Example 2 was diluted with ethylene glycol to a solid content concentration of 0.5% by weight to prepare a surface modifier.
  • Example 12 The polymer solution obtained in Example 2 was diluted with propylene glycol to a solid content concentration of 0.5% by weight to prepare a surface modifier.
  • Example 13 The polymer solution obtained in Example 2 was diluted with acetone to a solid content concentration of 0.5% by weight to prepare a surface modifier.
  • Example 14 The polymer solution obtained in Example 2 was diluted with n-hexane to a solid content concentration of 0.5% by weight to prepare a surface modifier.
  • a polymer solution was prepared using 36 g (0.09 mol). The polymer solution thus obtained had a solid content concentration of 31.7% by weight. Next, using the obtained polymer solution, a solid content concentration of 0.5% by weight in a mixed solvent composed of petroleum solvent (mineral terpene), C9 to C12 paraffin: C 9 to C 10 alkylbenzene (weight ratio 70:30) The surface modifier was prepared.
  • a mixed solvent composed of petroleum solvent (mineral terpene), C9 to C12 paraffin: C 9 to C 10 alkylbenzene weight ratio 70:30
  • a polymer solution was prepared using 37 g (0.09 mol). The polymer solution thus obtained had a solid content concentration of 31.1% by weight. Next, using the obtained polymer solution, a solid content concentration of 0.5% by weight with a mixed solvent composed of petroleum solvent (mineral terpene), C9 to C12 paraffin: C 9 to C 10 alkylbenzene (weight ratio 70:30) The surface modifier was prepared.
  • the surface modifier obtained in each of the above examples and comparative examples is dipped in cotton cloth, cotton / polyester blended cloth, polyester cloth, nylon cloth, water repellency (JIS L1092 compliant) and oil repellency. (AATCC-TM118 compliant) was measured.
  • the wet bag pickup after squeezing at that time was 110% cotton cloth, 75% cotton / polyester blended cloth, 115% polyester cloth, and 45% nylon cloth. Drying and curing were performed at 80 ° C. for 10 minutes.
  • Example 15 (1) In Example 1, (1), CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) I (99.8GC%) as a fluoroalkyl iodide Using 603 g (1.17 mol), changing the amount of tertiary butyl peroxide to 7 g, carrying out a reaction to introduce ethylene 49 g (1.7 mol), CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) I (98.3GC%) 635 g (98.8% yield) was obtained.
  • the reaction product was distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 100 to 144 ° C., and a tower top temperature of 58 to 59 ° C. to obtain 43.7 g of a purified reaction product (95.4 GC%) (distillation yield 88.2%) Got.
  • the obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
  • reaction mixture was cooled to recover 72 g of the reaction solution, and 44.5 g of the residue from which toluene was removed with an evaporator was washed with tap water, and a reaction product (86.3 GC%) that was a colorless and transparent liquid at room temperature was used as the lower layer 40.9 g (yield 82.6%) was obtained.
  • the reaction product was distilled under reduced pressure under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 103 to 143 ° C, and a tower top temperature of 60 to 61 ° C, and purified reaction product (99.2GC%) 15.7g (distillation yield 44.1%) Got.
  • copolymer solution having a solid content concentration of 19.6% by weight.
  • the weight average molecular weight Mw of the obtained fluorinated copolymer was measured in the same manner as in Example 1 (4), and found to be 38,000.
  • the copolymerization ratio measured by 1 H-NMR was 40.3% by mole of BzMA in the copolymer.
  • Example 16 In Example 15 (4), the same molar amount of stearyl methacrylate was used in place of benzyl methacrylate to obtain a copolymer solution having a solid content concentration of 19.6% by weight.
  • the fluorine-containing copolymer obtained here had a weight average molecular weight Mw of 34,000.
  • the copolymerization ratio measured by 1 H-NMR was 25.6 mol% of StMA in the copolymer.
  • copolymer solutions obtained in the above Examples 15 to 16 were diluted to a solid content concentration of 2% by weight using ethyl acetate, which is a polymerization solvent used in the polymerization, to give water / oil repellency (oil barrier properties).
  • ethyl acetate which is a polymerization solvent used in the polymerization
  • the static contact angle which is one index of
  • Table 2 Static contact angle Example Decane water oil diffusion test (%) 15 66 ° 117 ° 0 16 66 ° 117 ° 0
  • the stainless steel plate before the treatment with the diluting solution of the copolymer solution obtained in Examples 15 to 16 has a static contact angle with decane of 10 ° and a static contact angle with water of 90 °. Therefore, it was shown that the surface tension of the stainless steel surface is increased by performing the surface treatment using these diluents.

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Abstract

L'invention porte sur un agent de modification de surface préparé par dispersion d'un polymère fluoré dans un solvant organique non fluoré, le polymère fluoré comprenant 5 à 100 % en poids (en termes d'unités de polymérisation) d'un dérivé d'acide (méth)acrylique d'un alcool fluoroalkylique contenant un groupe perfluoroalkyle ayant au plus 6 atomes de carbone, ledit dérivé d'acide (méth)acrylique étant représenté par la formule générale : CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)c OCOCR=CH2 [dans laquelle R est un atome d'hydrogène ou un groupe méthyle ; n est un entier de 1 à 6 ; a est un entier de 1 à 4 ; b est entier de 1 à 3 ; et c est entier de 1 à 3]. D'ailleurs, un composé contenant un groupe perfluoroalkyle ayant au plus 6 atomes de carbone a la réputation d'être moins bioaccumulable. Des points de vue de la stabilité d'un fluide de polymérisation pendant la polymérisation, la solubilité et la vitesse de polymérisation, il est préférable que n soit un entier de 2 à 4 ; a soit un entier de 1 à 2 ; b soit un entier de 1 à 3 ; et c soit un entier de 1 à 2.
PCT/JP2010/053113 2009-03-04 2010-02-26 Agent de modification de surface contenant un polymère fluoré comme composant actif Ceased WO2010101091A1 (fr)

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WO2013088902A1 (fr) 2011-12-12 2013-06-20 ユニマテック株式会社 Copolymère fluoré et agent hydrofuge/oléofuge le comprenant comme principe actif
KR20140146165A (ko) * 2012-04-06 2014-12-24 닛토덴코 가부시키가이샤 발유성이 부여된 점착층을 구비한 통기 필터
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KR20170116057A (ko) 2015-02-13 2017-10-18 유니마테크 가부시키가이샤 함불소 공중합체 및 이것을 유효 성분으로 하는 표면개질제
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EP3444314A4 (fr) * 2016-04-15 2019-12-25 Agc Inc. Composition hydrofuge et procédé servant à la production d'un article doté d'un film imperméable à l'eau et perméable à l'humidité
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