WO2012074055A1 - Surface-modified extrusion-molded film - Google Patents

Surface-modified extrusion-molded film Download PDF

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WO2012074055A1
WO2012074055A1 PCT/JP2011/077805 JP2011077805W WO2012074055A1 WO 2012074055 A1 WO2012074055 A1 WO 2012074055A1 JP 2011077805 W JP2011077805 W JP 2011077805W WO 2012074055 A1 WO2012074055 A1 WO 2012074055A1
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monomer
meth
extruded film
film according
acrylate
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PCT/JP2011/077805
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French (fr)
Japanese (ja)
Inventor
昌隆 杉本
将幸 原口
元信 松山
理 上杉
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日産化学工業株式会社
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Priority to JP2012546934A priority Critical patent/JP5930971B2/en
Publication of WO2012074055A1 publication Critical patent/WO2012074055A1/en

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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92009—Measured parameter
    • B29C2948/92285—Surface properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9278—Surface properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0093—Other properties hydrophobic
    • 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
    • C08J2333/00—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
    • C08J2333/04—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
    • C08J2333/06—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 only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/20—Polymers characterized by their physical structure
    • C08J2400/202—Dendritic macromolecules, e.g. dendrimers or hyperbranched polymers
    • 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
    • C08J2433/06—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 only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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 surface-modified extruded film obtained by extrusion molding a resin composition to which a fluoroalkyl group-containing hyperbranched polymer is added.
  • Polymer (polymer) materials are increasingly used in many fields in recent years. Along with this, the characteristics of the surface and interface of the polymer as a matrix, as well as the properties of the polymer, have become important for each field. For example, by using a fluorine compound with low surface energy as a surface modifier, water and oil repellency, antifouling properties, non-adhesiveness, peelability, release properties, slipperiness, wear resistance, antireflection Various improvements relating to surface / interface control such as characteristics and chemical resistance are expected and various proposals have been made.
  • Patent Document 1 A method of surface-treating a film or sheet formed by extrusion molding with a fluorine-based polymer, a method of obtaining a sheet whose surface is treated with a fluorine-based polymer by coextrusion molding of an acrylic resin and polyvinylidene fluoride (Patent Document 1)
  • Patent Document 2 A method in which a fluorine-based polymer dissolved in a solvent is applied on a polyethylene terephthalate film is known.
  • the film thus obtained is used as a base material for adhesive sheets for indoor and outdoor use, a covering sheet, a release film for printed wiring boards, and the like.
  • Patent Document 3 a method of obtaining a surface-modified polycarbonate film by adding a small amount of a polycarbonate oligomer containing a fluoroalkyl group having a low surface energy to polycarbonate and performing extrusion molding.
  • Patent Document 3 the localization ratio of the fluorine-containing oligomer near the surface of the polycarbonate film is low, and it is still difficult to obtain sufficient surface modification.
  • this document only proposes the formulation of polycarbonate oligomers containing fluoroalkyl groups for surface modification of polycarbonate films.
  • Patent Document 4 As one surface modification method of a polymer, there is known a method in which a branched polymer is added to a matrix polymer composed of a linear polymer, and the branched polymer is concentrated on the surface of the matrix polymer (Patent Document 4).
  • Patent Document 1 and Patent Document 2 require coextrusion molding and application of a surface modifier, The process became complicated and industrially disadvantageous.
  • Patent Document 3 can modify the surface of an extruded film in a simple process, it does not specifically disclose the degree of transparency that is imparted when imparting transparency. That is, there has been a demand for a surface-modified extruded film having excellent water and oil repellency, transparency, and simple production.
  • the present inventor has (a) a monomer A having two or more radical polymerizable double bonds in the molecule, a fluoroalkyl group and at least 1 in the molecule.
  • a polymerization initiator C in an amount of 5 to 200 mol% with respect to the number of moles of the monomer A
  • the present invention provides, as a first aspect, (a) a monomer A having two or more radical polymerizable double bonds in the molecule, a fluoroalkyl group and at least one radical polymerizable double bond in the molecule.
  • a fluorine-containing hyperbranched polymer obtained by polymerizing a monomer B having a molecular weight of 5 to 200 mol% with respect to the number of moles of the monomer A, and (b) heat
  • the present invention relates to a surface-modified extruded film obtained by extruding a resin composition containing a plastic resin.
  • the present invention relates to the extruded film according to the first aspect, wherein the monomer A is a compound having at least one of a vinyl group and a (meth) acryl group.
  • the said monomer A is related with the extrusion-molded film as described in a 2nd viewpoint which is a divinyl compound or a di (meth) acrylate compound.
  • the present invention relates to the extruded film according to the third aspect, in which the monomer A is ethylene glycol di (meth) acrylate.
  • the present invention relates to the extruded film according to the first aspect obtained by using the monomer B in an amount of 5 to 300 mol% with respect to the number of moles of the monomer A.
  • the present invention relates to the extruded film according to the fifth aspect, wherein the monomer B is a compound having at least one of either a vinyl group or a (meth) acryl group.
  • the present invention relates to the extruded film according to the sixth aspect, wherein the monomer B is a compound represented by the following formula [1].
  • the present invention relates to the extruded film according to the seventh aspect, wherein the monomer B is a compound represented by the following formula [2].
  • R 1 has the same meaning as defined in the formula [1]
  • X represents a hydrogen atom or a fluorine atom
  • m represents 1 or 2
  • n represents an integer of 0 to 5.
  • the present invention relates to the extruded film according to any one of the first aspect to the eighth aspect, wherein the polymerization initiator C is an azo polymerization initiator.
  • the invention relates to the extruded film according to the ninth aspect, in which the polymerization initiator C is dimethyl 2,2′-azobisisobutyrate.
  • the content of the (a) fluorine-containing highly branched polymer is 0.01 to 20 parts by mass with respect to 100 parts by mass of the (b) thermoplastic resin. It is related with the extrusion-molded film as described in any one of them.
  • the present invention relates to the extruded film according to any one of the first aspect to the eleventh aspect, in which the thermoplastic resin (b) is polymethyl methacrylate.
  • any one of the first to twelfth aspects characterized in that the content ratio of the (a) fluorine-containing highly branched polymer is higher in the surface portion of the film than in the inside of the film.
  • the present invention relates to the extruded film according to one item.
  • the present invention relates to the extruded film according to any one of the first aspect to the thirteenth aspect, wherein the film has a thickness of 0.01 to 2.0 mm.
  • a monomer A having two or more radical polymerizable double bonds in the molecule and a monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule
  • a fluorine-containing highly branched polymer obtained by polymerizing in the presence of a polymerization initiator C in an amount of 5 to 200 mol% based on the number of moles of the monomer A
  • a thermoplastic resin relates to a method for producing a surface-modified extruded film, which comprises extruding a composition.
  • Fluorine-containing hyperbranched polymers are positively introduced with a branched structure, so there is less entanglement between molecules compared to linear polymers, and they exhibit fine particle behavior and are highly dispersible in resins. For this reason, in the resin which is a matrix, aggregation of the fluorine-containing highly branched polymer is prevented, and further, it easily moves to the surface and easily imparts activity to the resin surface. Therefore, even when a fluoroalkyl group having a short carbon chain is used, surface modification can be performed with a high effect. That is, by adding a fluorine-containing highly branched polymer to the resin composition, water / oil repellency and transparency can be imparted to the extruded film of the resin composition.
  • FIG. 1 is a diagram showing a 1 H NMR spectrum of a hyperbranched polymer 1 synthesized in Synthesis Example 1.
  • FIG. 3 is a diagram showing a 13 C NMR spectrum of hyperbranched polymer 1 synthesized in Synthesis Example 1.
  • FIG. 4 is a diagram showing a 1 H NMR spectrum of hyperbranched polymer 2 synthesized in Synthesis Example 2.
  • FIG. 6 is a diagram showing a 13 C NMR spectrum of hyperbranched polymer 2 synthesized in Synthesis Example 2.
  • FIG. 3 is a diagram showing a 1 H NMR spectrum of a linear polymer 1 synthesized in Synthesis Example 3.
  • FIG. 6 is a diagram showing a 13 C NMR spectrum of the linear polymer 1 synthesized in Synthesis Example 3.
  • the extruded film of the present invention comprises (a) a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule.
  • Fluorine-containing hyperbranched polymer obtained by polymerizing B in the presence of a polymerization initiator C in an amount of 5 to 200 mol% with respect to the number of moles of the monomer A, and (b) a thermoplastic resin, It is obtained by extruding a resin composition containing
  • the (a) fluorine-containing highly branched polymer includes a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule.
  • B is a polymer obtained by polymerizing B in the presence of a polymerization initiator C in an amount of 5 to 200 mol% based on the number of moles of the monomer A.
  • the fluorine-containing highly branched polymer is a so-called initiator fragment-incorporating type fluorine-containing highly branched polymer, and has a polymerization initiator C fragment used for polymerization at its terminal.
  • the monomer A is a monomer having two or more radically polymerizable double bonds in the molecule, and preferably has at least one of a vinyl group or a (meth) acryl group, and particularly a divinyl compound or di ( A meth) acrylate compound is preferred.
  • the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
  • (meth) acrylic acid refers to acrylic acid and methacrylic acid.
  • Examples of the monomer A include organic compounds shown in the following (A1) to (A7).
  • Nitrogen-containing vinyl compounds Diallylamine, diallyl isocyanurate, diallyl cyanurate, methylene bis (meth) acrylamide, bismaleimide, etc.
  • silicon-containing vinyl compounds Dimethyldivinylsilane, divinylmethylphenylsilane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetraphenyldisilazane
  • fluorine-containing vinyl compounds such as dietoxydivinylsilane: 1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, 1,8-divinylperfluorooctane and the like.
  • aromatic vinyl hydrocarbons of the group (A1-3) vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones of the group (A2), and (meth) acrylic acids of the group (A3).
  • An ester a vinyl compound having a polyalkylene glycol chain of (A4) group, and a nitrogen-containing vinyl compound of (A5) group. More preferably, divinylbenzene belonging to group (A1-3), diallyl phthalate belonging to group (A2-2), ethylene glycol di (meth) acrylate belonging to group (A3), 1,3-adamantane dimethanol dimer.
  • divinylbenzene, ethylene glycol di (meth) acrylate, and tricyclo [5.2.1.0 2,6 ] decanedimethanol di (meth) acrylate are preferable, and ethylene glycol di (meth) acrylate is particularly preferable. .
  • the monomer B is a monomer having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule, and preferably has at least one of either a vinyl group or a (meth) acryl group.
  • Particularly preferred are compounds represented by the following formula [1] or formula [2].
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a fluoroalkyl group having 2 to 12 carbon atoms.
  • R 1 has the same meaning as defined in the formula [1]
  • X represents a hydrogen atom or a fluorine atom
  • m represents 1 or 2
  • n represents an integer of 0 to 5.
  • Examples of the monomer B include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluorobutyl) ethyl (meth).
  • the ratio of copolymerizing the monomer A and the monomer B is preferably 5 to 300 mol% of the monomer B with respect to the number of moles of the monomer A, from the viewpoint of reactivity and surface modification effect.
  • the amount is preferably 10 to 150 mol%, more preferably 20 to 100 mol%.
  • an azo polymerization initiator is preferably used.
  • the azo polymerization initiator include compounds shown in the following (1) to (6).
  • Azonitrile compound 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis ( 1-cyclohexanecarbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile and the like;
  • Azoamide compound 2,2′-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide ⁇ , 2,2′-azobis ⁇ 2-methyl-N- [2- ( 1-hydroxybutyl)] propionamide ⁇ , 2,2′-azobis [2-methyl-N- (2-
  • azo polymerization initiators those having a substituent having a relatively low polarity are preferable from the viewpoint of the surface energy of the resulting fluorine-containing highly branched polymer, and in particular, dimethyl 2,2′-azobisisobutyrate or 2,2 ′ -Azobis (2,4,4-trimethylpentane) is preferred.
  • the polymerization initiator C is used in an amount of 5 to 200 mol%, preferably 15 to 200 mol%, more preferably 15 to 170 mol%, and most preferably 20 to 20 mol%, based on the number of moles of the monomer A. Used in an amount of 100 mol%.
  • the fluorine-containing hyperbranched polymer is obtained by polymerizing the monomer A and the monomer B in the presence of a predetermined amount of a polymerization initiator C with respect to the monomer A.
  • a polymerization initiator C for example, solution polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization and the like can be mentioned, and among these, solution polymerization or precipitation polymerization is preferable.
  • organic solvents used here include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane Solvent: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and other ester-based or ester ether-based solvents; diethyl ether, tetrahydrofuran, 1,4-
  • aromatic hydrocarbon solvents preferred are aromatic hydrocarbon solvents, halogen solvents, ester solvents or ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, etc.
  • aromatic hydrocarbon solvents preferred are toluene, xylene, orthodichlorobenzene, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 1,4-dioxane, methyl cellosolve, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethyl Acetamide and the like.
  • the content of the organic solvent in the entire polymerization reaction product is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 1 part by weight of the monomer A. It is.
  • the polymerization reaction is carried out under normal pressure, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Further, preferably carried out in an atmosphere of inert gas such as N 2.
  • the temperature of the polymerization reaction is preferably 50 to 200 ° C, more preferably 70 to 150 ° C. More preferably, the temperature of the polymerization reaction is carried out at a temperature 20 ° C.
  • the polymerization reaction is preferably carried out by dropping a solution containing the organic solvent into the organic solvent maintained at a temperature 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator C. It is even more preferable to carry out the polymerization reaction at the reflux temperature of the organic solvent under a reaction pressure.
  • the obtained fluorine-containing hyperbranched polymer is collected by an arbitrary method, and post-treatment such as washing is performed as necessary. Examples of a method for recovering the polymer from the reaction solution include a method such as reprecipitation.
  • the weight average molecular weight (hereinafter abbreviated as Mw) of the obtained fluorine-containing highly branched polymer is preferably 1,000 to 200,000, more preferably 2,000 to 100, in terms of polystyrene by gel permeation chromatography (GPC). 5,000, most preferably 5,000 to 60,000.
  • the thermoplastic resin is not particularly limited.
  • a polyolefin resin such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer);
  • Polystyrene resins such as PS (polystyrene), HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer)
  • Polycarbonate resin polyamide resin; polyimide resin; (meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate Polybutylene naphthalate, PLA (polylactic acid), poly-3-hydroxybutyric acid,
  • the amount of the (a) fluorine-containing highly branched polymer is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 100 parts by mass of the (b) thermoplastic resin. To 20 parts by mass, and more preferably 0.1 to 10 parts by mass.
  • Additives generally added to the resin composition together with the thermoplastic resin such as antistatic agents, lubricants, thermal stabilizers, antioxidants, light stabilizers, fluorescent agents, processing aids, crosslinking agents, dispersants , Foaming agents, flame retardants, antifoaming agents, reinforcing agents, pigments, and the like may be used in combination.
  • extruded film The extruded film of the present invention is blended with the above-mentioned (a) fluorine-containing hyperbranched polymer and (b) thermoplastic resin and melt-kneaded. In some cases, other desired components are blended and melt-kneaded. Can be obtained by the extrusion molding method.
  • the thickness of the extruded film is not particularly limited, but is usually 0.01 to 2.0 mm, preferably 0.01 to 1.5 mm, and more preferably 0.01 to 1.0 mm.
  • the extruded film of the present invention is in a state in which more of the fluorine-containing highly branched polymer is present on the surface (interface) portion of the film than in the inside (deep portion) of the film.
  • the extrusion-molded film of the present invention is a film excellent in peelability from other resin films such as a film, and further in water / oil repellency and transparency.
  • Solvent (2.7 mmol Na 2 CO 3 + 0.3 mmol NaHCO 3 ) / L aqueous solution
  • Detector Electrical conductivity
  • Spin coater Device MS-A100 manufactured by Mikasa Corporation (5) Ellipsometry (refractive index and film thickness measurement) Apparatus: J.M. A.
  • EGDMA Ethylene glycol dimethacrylate [1G made by Shin-Nakamura Chemical Co., Ltd.]
  • C6FA 2- (perfluorohexyl) ethyl acrylate [FAAC-6 manufactured by Unimatec Co., Ltd.]
  • MAIB Dimethyl 2,2′-azobisisobutyrate [MAIB manufactured by Otsuka Chemical Co., Ltd.]
  • MMA Methyl methacrylate [Wako Pure Chemical Industries, Ltd.]
  • THF Tetrahydrofuran
  • MEK Methyl ethyl ketone
  • PGMEA Propylene glycol monomethyl ether acetate
  • the contents were added dropwise from the 100 mL reaction flask charged with EGDMA, C6FA and MAIB to the refluxed toluene in the 200 mL reaction flask using a dropping pump over 30 minutes. After completion of dropping, the mixture was aged for 1 hour. Next, this reaction liquid was added to 277 g of hexane / toluene (mass ratio 4: 1) to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure, redissolved using 36 g of THF, and a THF solution of this polymer was added to 277 g of hexane to reprecipitate the polymer in a slurry state.
  • the contents were added dropwise from the 100 mL reaction flask charged with EGDMA, C6FA and MAIB to the refluxed toluene in the 200 mL reaction flask using a dropping pump over 30 minutes. After completion of dropping, the mixture was aged for 1 hour. Next, 75 g of toluene was distilled off from this reaction solution using a rotary evaporator, and then added to 278 g of hexane to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and vacuum dried to obtain 4.4 g of the target product (highly branched polymer 2) as a white powder (43% yield).
  • the 1 H NMR and 13 C NMR spectra of the obtained target product are shown in FIGS. 3 and 4. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 6,800, and dispersion degree: Mw / Mn was 1.9.
  • the atomic content is shown in Table 1.
  • Example 1 Production of hyperbranched polymer-added PMMA masterbatch 10 g of hyperbranched polymer 1 or hyperbranched polymer 2 and 40 g of PMMA were kneaded at a temperature of 230 ° C and a rotation speed of 50 rpm for 5 minutes using a simple kneader. A PMMA master batch having a branched polymer concentration of 20% by mass was prepared.
  • Example 2 Production of highly branched polymer-added PMMA extruded film
  • the highly branched polymer concentration in the highly branched polymer-containing PMMA was adjusted to the concentration shown in Table 3 in a twin-screw kneading extruder.
  • the prepared master batch and PMMA were added, and an extrusion-molded film was prepared under the conditions shown in Table 3 for a screw rotation speed of 100 rpm, a discharge rate of 2 g / min, a die width of 20 mm, and a die lip interval of 0.8 mm.
  • the contact angle of water and hexadecane of the obtained film was evaluated. The obtained results are shown in Table 3 together.
  • the PMMA films (Examples 2 to 19) to which the hyperbranched polymer was added had a water contact angle of 81.5 to 101.9 degrees and a hexadecane contact angle of 35.2 to 57.0 degrees. Both showed high contact angles. From this result, it was revealed that liquid repellency was imparted to the PMMA extruded film by adding a hyperbranched polymer to the PMMA extruded film.
  • the linear polymer-added PMMA extruded film (Comparative Examples 2 to 5) had low transparency.
  • the highly branched polymer-added PMMA extruded films (Examples 13 to 18) were excellent in transparency. From this result, it became clear that even if a highly branched polymer was added to the PMMA extruded film, the original transparency of the PMMA extruded film was not impaired.

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Abstract

[Problem] To provide an extrusion-molded film having excellent water-repellent/oil-repellent properties and excellent transparency. [Solution] A surface-modified extrusion-molded film produced by the extrusion molding of a resin composition comprising: (a) a fluorinated hyperbranched polymer produced by polymerizing a monomer (A) having at least two radically polymerizable double bonds in the molecule and a monomer (B) having a fluoroalkyl group and at least one radically polymerizable double bond in the molecule in the presence of a polymerization initiator (C) in an amount of 5-200 mol% relative to the molar number of the monomer (A); and (b) a thermoplastic resin.

Description

表面改質された押出成形フィルムSurface modified extrusion film
　本発明は、フルオロアルキル基含有高分岐ポリマーを添加した樹脂組成物を押出成形することで得られる、表面改質された押出成形フィルムに関する。 The present invention relates to a surface-modified extruded film obtained by extrusion molding a resin composition to which a fluoroalkyl group-containing hyperbranched polymer is added.
　ポリマー（高分子）材料は、近年、多分野でますます利用されている。それに伴い、それぞれの分野に応じて、マトリクスとしてのポリマーの性状とともに、その表面や界面の特性が重要となっている。例えば、表面エネルギーの低いフッ素系化合物を表面改質剤として用いることにより、撥水・撥油性、防汚性、非粘着性、剥離性、離型性、滑り性、耐磨耗性、反射防止特性、耐薬品性などの表面・界面制御に関する特性の向上が期待され、種々提案されている。 Polymer (polymer) materials are increasingly used in many fields in recent years. Along with this, the characteristics of the surface and interface of the polymer as a matrix, as well as the properties of the polymer, have become important for each field. For example, by using a fluorine compound with low surface energy as a surface modifier, water and oil repellency, antifouling properties, non-adhesiveness, peelability, release properties, slipperiness, wear resistance, antireflection Various improvements relating to surface / interface control such as characteristics and chemical resistance are expected and various proposals have been made.
　押出成形により成形されたフィルム・シートをフッ素系ポリマーで表面処理する方法として、アクリル樹脂とポリフッ化ビニリデンの共押出成形により、表面がフッ素系ポリマーで処理されたシートを得る方法（特許文献１）、ポリエチレンテレフタレートフィルム上に、溶剤に溶解したフッ素系ポリマーを塗布する方法（特許文献２）が知られている。このようにして得られたフィルムは、屋内・屋外用の粘着シートの基材、被覆用シート、プリント配線板の離型フィルムなどに用いられる。
　また、ポリカーボネートに表面エネルギーの低いフルオロアルキル基を含有するポリカーボネートオリゴマーを少量添加し、押出成形することにより、表面改質されたポリカーボネートフィルムを得る方法が開示されている（特許文献３）。しかし、この方法では、ポリカーボネートフィルムの表面近傍への含フッ素オリゴマーの局在化の割合が低く、未だ十分な表面改質が得られにくい。しかも、この文献は、ポリカーボネートフィルムの表面改質のためにフルオロアルキル基を含有するポリカーボネートオリゴマーの配合を提案するにとどまる。
　一方、ポリマーの表面改質方法の一つとして、線状ポリマーからなるマトリクスポリマーに分岐ポリマーを添加し、該分岐ポリマーを該マトリクスポリマー表面に濃縮させる方法が知られている（特許文献４）。 As a method of surface-treating a film or sheet formed by extrusion molding with a fluorine-based polymer, a method of obtaining a sheet whose surface is treated with a fluorine-based polymer by coextrusion molding of an acrylic resin and polyvinylidene fluoride (Patent Document 1) A method (Patent Document 2) in which a fluorine-based polymer dissolved in a solvent is applied on a polyethylene terephthalate film is known. The film thus obtained is used as a base material for adhesive sheets for indoor and outdoor use, a covering sheet, a release film for printed wiring boards, and the like.
Also disclosed is a method of obtaining a surface-modified polycarbonate film by adding a small amount of a polycarbonate oligomer containing a fluoroalkyl group having a low surface energy to polycarbonate and performing extrusion molding (Patent Document 3). However, in this method, the localization ratio of the fluorine-containing oligomer near the surface of the polycarbonate film is low, and it is still difficult to obtain sufficient surface modification. Moreover, this document only proposes the formulation of polycarbonate oligomers containing fluoroalkyl groups for surface modification of polycarbonate films.
On the other hand, as one surface modification method of a polymer, there is known a method in which a branched polymer is added to a matrix polymer composed of a linear polymer, and the branched polymer is concentrated on the surface of the matrix polymer (Patent Document 4).
特開平７－３２９２５５号公報JP 7-329255 A 特開２００８－１６２２２２号公報JP 2008-162222 A 特表２００７－５１４７１０号公報Special table 2007-514710 gazette 国際公開第２００７／０４９６０８号パンフレットInternational Publication No. 2007/0449608 Pamphlet
　上述の通り、押出成形フィルムにおける種々の表面改質方法が提案されているが、特許文献１及び特許文献２に示す手法では、共押出成形や表面改質剤の塗布が必要であることから、工程が煩雑となり工業的に不利であった。また、特許文献３に示す手法では、簡便な工程で押出成形フィルムを表面改質できるものの、その透明性付与において、付与される透明度の程度について具体的には開示されていない。
　すなわち、撥水・撥油性に優れ、さらに透明性を有し、しかも簡便に製造できる表面改質された押出成形フィルムが求められていた。 As described above, various surface modification methods for extrusion-molded films have been proposed, but the methods shown in Patent Document 1 and Patent Document 2 require coextrusion molding and application of a surface modifier, The process became complicated and industrially disadvantageous. Moreover, although the method shown in Patent Document 3 can modify the surface of an extruded film in a simple process, it does not specifically disclose the degree of transparency that is imparted when imparting transparency.
That is, there has been a demand for a surface-modified extruded film having excellent water and oil repellency, transparency, and simple production.
　本発明者は、上記目的を達成するために鋭意検討を重ねた結果、（ａ）分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にフルオロアルキル基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＢとを、該モノマーＡのモル数に対して、５～２００モル％の量の重合開始剤Ｃの存在下で重合させることにより得られる含フッ素高分岐ポリマー、及び（ｂ）熱可塑性樹脂、を含む樹脂組成物を押出成形することによって得られる押出成形フィルムが、撥水・撥油性に優れ、透明性を有し、さらに簡便に製造できることを見出し、本発明を完成させた。
　すなわち、本発明は、第１観点として、（ａ）分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にフルオロアルキル基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＢとを、該モノマーＡのモル数に対して、５～２００モル％の量の重合開始剤Ｃの存在下で重合させることにより得られる含フッ素高分岐ポリマー、及び（ｂ）熱可塑性樹脂、を含む樹脂組成物を押出成形することによって得られる表面改質された押出成形フィルムに関する。
　第２観点として、前記モノマーＡがビニル基又は（メタ）アクリル基の何れか一方を少なくとも１つ有する化合物である、第１観点に記載の押出成形フィルムに関する。
　第３観点として、前記モノマーＡがジビニル化合物又はジ（メタ）アクリレート化合物である、第２観点に記載の押出成形フィルムに関する。
　第４観点として、前記モノマーＡがエチレングリコールジ（メタ）アクリレートである、第３観点に記載の押出成形フィルムに関する。
　第５観点として、前記モノマーＡのモル数に対して５～３００モル％の量の前記モノマーＢを用いて得られる、第１観点に記載の押出成形フィルムに関する。
　第６観点として、前記モノマーＢがビニル基又は（メタ）アクリル基の何れか一方を少なくとも１つ有する化合物である、第５観点に記載の押出成形フィルムに関する。
　第７観点として、前記モノマーＢが下記式［１］で表される化合物である、第６観点に記載の押出成形フィルムに関する。
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数２～１２のフルオロアルキル基を表す。）
　第８観点として、前記モノマーＢが下記式［２］で表される化合物である、第７観点に記載の押出成形フィルムに関する。
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ1は前記式［１］における定義と同じ意味を表し、Ｘは水素原子又はフッ素原子を表し、ｍは１又は２を表し、ｎは０～５の整数を表す。）
　第９観点として、前記重合開始剤Ｃがアゾ系重合開始剤である、第１観点乃至第８観点のうち何れか一項に記載の押出成形フィルムに関する。
　第１０観点として、前記重合開始剤Ｃが２，２'－アゾビスイソ酪酸ジメチルである、第９観点に記載の押出成形フィルムに関する。
　第１１観点として、前記（ａ）含フッ素高分岐ポリマーの含有量が、前記（ｂ）熱可塑性樹脂１００質量部に対して０．０１乃至２０質量部である、第１観点乃至第１０観点のうち何れか一項に記載の押出成形フィルムに関する。
　第１２観点として、前記（ｂ）熱可塑性樹脂がポリメチルメタクリレートである、第１観点乃至第１１観点のうち何れか一項に記載の押出成形フィルムに関する。
　第１３観点として、フィルムの内部に比べて、該フィルムの表面部において前記（ａ）含フッ素高分岐ポリマーの含有割合がより高いことを特徴とする、第１観点乃至第１２観点のうち何れか一項に記載の押出成形フィルムに関する。
　第１４観点として、フィルムの厚さが０．０１～２．０ｍｍである、第１観点乃至第１３観点のうち何れか一項に記載の押出成形フィルムに関する。
　第１５観点として、（ａ）分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にフルオロアルキル基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＢとを、該モノマーＡのモル数に対して、５～２００モル％の量の重合開始剤Ｃの存在下で重合させることにより得られる含フッ素高分岐ポリマー、及び（ｂ）熱可塑性樹脂、を含む樹脂組成物を押出成形することを特徴とする、表面改質された押出成形フィルムの製造方法に関する。 As a result of intensive studies to achieve the above object, the present inventor has (a) a monomer A having two or more radical polymerizable double bonds in the molecule, a fluoroalkyl group and at least 1 in the molecule. The fluorine-containing polymer obtained by polymerizing the monomer B having one radical polymerizable double bond in the presence of a polymerization initiator C in an amount of 5 to 200 mol% with respect to the number of moles of the monomer A It has been found that an extruded film obtained by extruding a resin composition containing a branched polymer and (b) a thermoplastic resin is excellent in water and oil repellency, has transparency, and can be produced more easily. The present invention has been completed.
That is, the present invention provides, as a first aspect, (a) a monomer A having two or more radical polymerizable double bonds in the molecule, a fluoroalkyl group and at least one radical polymerizable double bond in the molecule. A fluorine-containing hyperbranched polymer obtained by polymerizing a monomer B having a molecular weight of 5 to 200 mol% with respect to the number of moles of the monomer A, and (b) heat The present invention relates to a surface-modified extruded film obtained by extruding a resin composition containing a plastic resin.
As a second aspect, the present invention relates to the extruded film according to the first aspect, wherein the monomer A is a compound having at least one of a vinyl group and a (meth) acryl group.
As a 3rd viewpoint, the said monomer A is related with the extrusion-molded film as described in a 2nd viewpoint which is a divinyl compound or a di (meth) acrylate compound.
As a fourth aspect, the present invention relates to the extruded film according to the third aspect, in which the monomer A is ethylene glycol di (meth) acrylate.
As a fifth aspect, the present invention relates to the extruded film according to the first aspect obtained by using the monomer B in an amount of 5 to 300 mol% with respect to the number of moles of the monomer A.
As a sixth aspect, the present invention relates to the extruded film according to the fifth aspect, wherein the monomer B is a compound having at least one of either a vinyl group or a (meth) acryl group.
As a seventh aspect, the present invention relates to the extruded film according to the sixth aspect, wherein the monomer B is a compound represented by the following formula [1].
Figure JPOXMLDOC01-appb-C000003
 (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a fluoroalkyl group having 2 to 12 carbon atoms.)
As an eighth aspect, the present invention relates to the extruded film according to the seventh aspect, wherein the monomer B is a compound represented by the following formula [2].
Figure JPOXMLDOC01-appb-C000004
 (In the formula, R 1 has the same meaning as defined in the formula [1], X represents a hydrogen atom or a fluorine atom, m represents 1 or 2, and n represents an integer of 0 to 5.)
As a ninth aspect, the present invention relates to the extruded film according to any one of the first aspect to the eighth aspect, wherein the polymerization initiator C is an azo polymerization initiator.
As a tenth aspect, the invention relates to the extruded film according to the ninth aspect, in which the polymerization initiator C is dimethyl 2,2′-azobisisobutyrate.
As an eleventh aspect, the content of the (a) fluorine-containing highly branched polymer is 0.01 to 20 parts by mass with respect to 100 parts by mass of the (b) thermoplastic resin. It is related with the extrusion-molded film as described in any one of them.
As a twelfth aspect, the present invention relates to the extruded film according to any one of the first aspect to the eleventh aspect, in which the thermoplastic resin (b) is polymethyl methacrylate.
As a thirteenth aspect, any one of the first to twelfth aspects, characterized in that the content ratio of the (a) fluorine-containing highly branched polymer is higher in the surface portion of the film than in the inside of the film. The present invention relates to the extruded film according to one item.
As a fourteenth aspect, the present invention relates to the extruded film according to any one of the first aspect to the thirteenth aspect, wherein the film has a thickness of 0.01 to 2.0 mm.
As a fifteenth aspect, (a) a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule A fluorine-containing highly branched polymer obtained by polymerizing in the presence of a polymerization initiator C in an amount of 5 to 200 mol% based on the number of moles of the monomer A, and (b) a thermoplastic resin The present invention relates to a method for producing a surface-modified extruded film, which comprises extruding a composition.
　含フッ素高分岐ポリマーは、積極的に枝分かれ構造を導入しているため、線状高分子と比較して分子間の絡み合いが少なく、微粒子的挙動を示し樹脂に対する分散性が高い。このため、マトリクスである樹脂中において、含フッ素高分岐ポリマーの凝集を防ぎ、さらに、表面に移動しやすく、樹脂表面に活性を付与しやすい。従って、炭素鎖が短いフルオロアルキル基を使用した場合でも、高い効果で表面改質を行うことができる。すなわち、含フッ素高分岐ポリマーを樹脂組成物に添加することで、該樹脂組成物の押出成形フィルムに撥水・撥油性及び透明性を付与することができる。 Fluorine-containing hyperbranched polymers are positively introduced with a branched structure, so there is less entanglement between molecules compared to linear polymers, and they exhibit fine particle behavior and are highly dispersible in resins. For this reason, in the resin which is a matrix, aggregation of the fluorine-containing highly branched polymer is prevented, and further, it easily moves to the surface and easily imparts activity to the resin surface. Therefore, even when a fluoroalkyl group having a short carbon chain is used, surface modification can be performed with a high effect. That is, by adding a fluorine-containing highly branched polymer to the resin composition, water / oil repellency and transparency can be imparted to the extruded film of the resin composition.
合成例１で合成された高分岐ポリマー１の1Ｈ　ＮＭＲスペクトルを示す図である。1 is a diagram showing a 1 H NMR spectrum of a hyperbranched polymer 1 synthesized in Synthesis Example 1. FIG. 合成例１で合成された高分岐ポリマー１の13Ｃ　ＮＭＲスペクトルを示す図である。3 is a diagram showing a 13 C NMR spectrum of hyperbranched polymer 1 synthesized in Synthesis Example 1. FIG. 合成例２で合成された高分岐ポリマー２の1Ｈ　ＮＭＲスペクトルを示す図である。4 is a diagram showing a 1 H NMR spectrum of hyperbranched polymer 2 synthesized in Synthesis Example 2. FIG. 合成例２で合成された高分岐ポリマー２の13Ｃ　ＮＭＲスペクトルを示す図である。6 is a diagram showing a 13 C NMR spectrum of hyperbranched polymer 2 synthesized in Synthesis Example 2. FIG. 合成例３で合成された直鎖状ポリマー１の1Ｈ　ＮＭＲスペクトルを示す図である。3 is a diagram showing a 1 H NMR spectrum of a linear polymer 1 synthesized in Synthesis Example 3. FIG. 合成例３で合成された直鎖状ポリマー１の13Ｃ　ＮＭＲスペクトルを示す図である。6 is a diagram showing a 13 C NMR spectrum of the linear polymer 1 synthesized in Synthesis Example 3. FIG.
　本発明の押出成形フィルムは、（ａ）分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にフルオロアルキル基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＢとを、該モノマーＡのモル数に対して、５～２００モル％の量の重合開始剤Ｃの存在下で重合させることにより得られる含フッ素高分岐ポリマー、及び（ｂ）熱可塑性樹脂、を含む樹脂組成物を押出成形することによって得られる。 The extruded film of the present invention comprises (a) a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule. Fluorine-containing hyperbranched polymer obtained by polymerizing B in the presence of a polymerization initiator C in an amount of 5 to 200 mol% with respect to the number of moles of the monomer A, and (b) a thermoplastic resin, It is obtained by extruding a resin composition containing
［（ａ）含フッ素高分岐ポリマー］
　上記（ａ）含フッ素高分岐ポリマーは、分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にフルオロアルキル基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＢとを、該モノマーＡのモル数に対して、５～２００モル％の量の重合開始剤Ｃの存在下で重合させることにより得られるポリマーである。また（ａ）含フッ素高分岐ポリマーは、いわゆる開始剤断片組込み型含フッ素高分岐ポリマーであり、その末端に重合に使用した重合開始剤Ｃの断片を有している。 [(A) Fluorine-containing highly branched polymer]
The (a) fluorine-containing highly branched polymer includes a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule. B is a polymer obtained by polymerizing B in the presence of a polymerization initiator C in an amount of 5 to 200 mol% based on the number of moles of the monomer A. Further, (a) the fluorine-containing highly branched polymer is a so-called initiator fragment-incorporating type fluorine-containing highly branched polymer, and has a polymerization initiator C fragment used for polymerization at its terminal.
＜モノマーＡ＞
　モノマーＡは、分子内に２個以上のラジカル重合性二重結合を有するモノマーであり、ビニル基又は（メタ）アクリル基の何れか一方を少なくとも１つ有することが好ましく、特にジビニル化合物又はジ（メタ）アクリレート化合物であることが好ましい。
　なお、本発明では（メタ）アクリレート化合物とは、アクリレート化合物とメタクリレート化合物の両方をいう。例えば（メタ）アクリル酸は、アクリル酸とメタクリル酸をいう。 <Monomer A>
The monomer A is a monomer having two or more radically polymerizable double bonds in the molecule, and preferably has at least one of a vinyl group or a (meth) acryl group, and particularly a divinyl compound or di ( A meth) acrylate compound is preferred.
In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.
　前記モノマーＡとしては、例えば、以下の（Ａ１）～（Ａ７）に示す有機化合物が挙げられる。
（Ａ１）ビニル系炭化水素：
（Ａ１－１）脂肪族ビニル系炭化水素；イソプレン、ブタジエン、３－メチル－１，２－ブタジエン、２，３－ジメチル－１，３－ブタジエン、１，２－ポリブタジエン、ペンタジエン、ヘキサジエン、オクタジエン等
（Ａ１－２）脂環式ビニル系炭化水素；シクロペンタジエン、シクロヘキサジエン、シクロオクタジエン、ノルボルナジエン等
（Ａ１－３）芳香族ビニル系炭化水素；ジビニルベンゼン、ジビニルトルエン、ジビニルキシレン、トリビニルベンゼン、ジビニルビフェニル、ジビニルナフタレン、ジビニルフルオレン、ジビニルカルバゾール、ジビニルピリジン等
（Ａ２）ビニルエステル、アリルエステル、ビニルエーテル、アリルエーテル、ビニルケトン：
（Ａ２－１）ビニルエステル；アジピン酸ジビニル、マレイン酸ジビニル、フタル酸ジビニル、イソフタル酸ジビニル、イタコン酸ジビニル、ビニル（メタ）アクリレート等
（Ａ２－２）アリルエステル；マレイン酸ジアリル、フタル酸ジアリル、イソフタル酸ジアリル、アジピン酸ジアリル、アリル（メタ）アクリレート等
（Ａ２－３）ビニルエーテル；ジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル等
（Ａ２－４）アリルエーテル；ジアリルエーテル、ジアリルオキシエタン、トリアリルオキシエタン、テトラアリルオキシエタン、テトラアリルオキシプロパン、テトラアリルオキシブタン、テトラメタリルオキシエタン等
（Ａ２－５）ビニルケトン；ジビニルケトン、ジアリルケトン等
（Ａ３）（メタ）アクリル酸エステル：
エチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、アルコキシチタントリ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、２－メチル－１，８－オクタンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、トリシクロ[５．２．１．０２，６]デカンジメタノールジ（メタ）アクリレート、ジオキサングリコールジ（メタ）アクリレート、２－ヒドロキシ－１－アクリロイルオキシ－３－メタクリロイルオキシプロパン、２－ヒドロキシ－１，３－ジ（メタ）アクリロイルオキシプロパン、９，９－ビス［４－（２－（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン、ウンデシレノキシエチレングリコールジ（メタ）アクリレート、ビス［４－（メタ）アクリロイルチオフェニル］スルフィド、ビス［２－（メタ）アクリロイルチオエチル］スルフィド、１，３－アダマンタンジオールジ（メタ）アクリレート、１，３－アダマンタンジメタノールジ（メタ）アクリレート等
（Ａ４）ポリアルキレングリコール鎖を有するビニル系化合物：
ポリエチレングリコール（分子量３００）ジ（メタ）アクリレート、ポリプロピレングリコール（分子量５００）ジ（メタ）アクリレート等
（Ａ５）含窒素ビニル系化合物：
ジアリルアミン、ジアリルイソシアヌレート、ジアリルシアヌレート、メチレンビス（メタ）アクリルアミド、ビスマレイミド等
（Ａ６）含ケイ素ビニル系化合物：
ジメチルジビニルシラン、ジビニルメチルフェニルシラン、ジフェニルジビニルシラン、１，３－ジビニル－１，１，３，３－テトラメチルジシラザン、１，３－ジビニル－１，１，３，３－テトラフェニルジシラザン、ジエトキジビニルシラン等
（Ａ７）含フッ素ビニル系化合物：
１，４－ジビニルパーフルオロブタン、１，６－ジビニルパーフルオロヘキサン、１，８－ジビニルパーフルオロオクタン等。 Examples of the monomer A include organic compounds shown in the following (A1) to (A7).
(A1) Vinyl hydrocarbon:
(A1-1) Aliphatic vinyl hydrocarbons: isoprene, butadiene, 3-methyl-1,2-butadiene, 2,3-dimethyl-1,3-butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octadiene, etc. (A1-2) Alicyclic vinyl hydrocarbons; cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, etc. (A1-3) aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, Divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine, etc. (A2) Vinyl esters, allyl esters, vinyl ethers, allyl ethers, vinyl ketones:
(A2-1) Vinyl ester; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itaconate, vinyl (meth) acrylate, etc. (A2-2) allyl ester; diallyl maleate, diallyl phthalate, Diallyl isophthalate, diallyl adipate, allyl (meth) acrylate, etc. (A2-3) vinyl ether; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc. (A2-4) allyl ether; diallyl ether, diallyloxyethane, tri Allyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc. (A2-5) vinyl ketone; divinyl ketone, diallyl Tons, etc. (A3) (meth) acrylic acid ester:
Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, alkoxytitanium tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decanedimethanol di (meth) ) Acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, undecylenoxyethylene glycol di (meth) acrylate, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] (A4) Vinyl compounds having a polyalkylene glycol chain such as sulfide, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, etc .:
Polyethylene glycol (molecular weight 300) di (meth) acrylate, polypropylene glycol (molecular weight 500) di (meth) acrylate, etc. (A5) Nitrogen-containing vinyl compounds:
Diallylamine, diallyl isocyanurate, diallyl cyanurate, methylene bis (meth) acrylamide, bismaleimide, etc. (A6) silicon-containing vinyl compounds:
Dimethyldivinylsilane, divinylmethylphenylsilane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetraphenyldisilazane (A7) fluorine-containing vinyl compounds such as dietoxydivinylsilane:
1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, 1,8-divinylperfluorooctane and the like.
　これらのうち好ましいものは、上記（Ａ１－３）群の芳香族ビニル系炭化水素、（Ａ２）群のビニルエステル、アリルエステル、ビニルエーテル、アリルエーテル及びビニルケトン、（Ａ３）群の（メタ）アクリル酸エステル、（Ａ４）群のポリアルキレングリコール鎖を有するビニル系化合物、並びに（Ａ５）群の含窒素ビニル系化合物である。
　より好ましいのは、（Ａ１－３）群に属するジビニルベンゼン、（Ａ２－２）群に属するフタル酸ジアリル、（Ａ３）群に属するエチレングリコールジ（メタ）アクリレート、１，３－アダマンタンジメタノールジ（メタ）アクリレート、トリシクロ[５．２．１．０２，６]デカンジメタノールジ（メタ）アクリレート並びに（Ａ５）群に属するメチレンビス（メタ）アクリルアミドである。
　これらの中でもジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、及びトリシクロ[５．２．１．０２，６]デカンジメタノールジ（メタ）アクリレートが好ましく、特にエチレングリコールジ（メタ）アクリレートがより好ましい。 Among these, preferred are the above-mentioned aromatic vinyl hydrocarbons of the group (A1-3), vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones of the group (A2), and (meth) acrylic acids of the group (A3). An ester, a vinyl compound having a polyalkylene glycol chain of (A4) group, and a nitrogen-containing vinyl compound of (A5) group.
More preferably, divinylbenzene belonging to group (A1-3), diallyl phthalate belonging to group (A2-2), ethylene glycol di (meth) acrylate belonging to group (A3), 1,3-adamantane dimethanol dimer. (Meth) acrylate, tricyclo [5.2.1.0 2,6 ] decandimethanol di (meth) acrylate and methylene bis (meth) acrylamide belonging to group (A5).
Among these, divinylbenzene, ethylene glycol di (meth) acrylate, and tricyclo [5.2.1.0 2,6 ] decanedimethanol di (meth) acrylate are preferable, and ethylene glycol di (meth) acrylate is particularly preferable. .
＜モノマーＢ＞
　前記モノマーＢは、分子内にフルオロアルキル基及び少なくとも１個のラジカル重合性二重結合を有するモノマーであって、好ましくはビニル基又は（メタ）アクリル基の何れか一方を少なくとも１つ有することが好ましく、特に下記式［１］又は式［２］で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数２～１２のフルオロアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ1は前記式［１］における定義と同じ意味を表し、Ｘは水素原子又はフッ素原子を表し、ｍは１又は２を表し、ｎは０～５の整数を表す。） <Monomer B>
The monomer B is a monomer having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule, and preferably has at least one of either a vinyl group or a (meth) acryl group. Particularly preferred are compounds represented by the following formula [1] or formula [2].
Figure JPOXMLDOC01-appb-C000005
 (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a fluoroalkyl group having 2 to 12 carbon atoms.)
Figure JPOXMLDOC01-appb-C000006
 (In the formula, R 1 has the same meaning as defined in the formula [1], X represents a hydrogen atom or a fluorine atom, m represents 1 or 2, and n represents an integer of 0 to 5.)
　前記モノマーＢとしては、例えば２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３，３－ペンタフルオロプロピル（メタ）アクリレート、２－（パーフルオロブチル）エチル（メタ）アクリレート、２－（パーフルオロヘキシル）エチル（メタ）アクリレート、２－（パーフルオロオクチル）エチル（メタ）アクリレート、２－（パーフルオロデシル）エチル（メタ）アクリレート、２－（パーフルオロ－３－メチルブチル）エチル（メタ）アクリレート、２－（パーフルオロ－５－メチルヘキシル）エチル（メタ）アクリレート、２－（パーフルオロ－７－メチルオクチル）エチル（メタ）アクリレート、１Ｈ，１Ｈ，３Ｈ－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、１Ｈ，１Ｈ，７Ｈ－ドデカフルオロヘプチル（メタ）アクリレート、１Ｈ，１Ｈ，９Ｈ－ヘキサデカフルオロノニル（メタ）アクリレート、１Ｈ－１－（トリフルオロメチル）トリフルオロエチル（メタ）アクリレート、１Ｈ，１Ｈ，３Ｈ－ヘキサフルオロブチル（メタ）アクリレート、３－パーフルオロブチル－２－ヒドロキシプロピル（メタ）アクリレート、３－パーフルオロヘキシル－２－ヒドロキシプロピル（メタ）アクリレート、３－パーフルオロオクチル－２－ヒドロキシプロピル（メタ）アクリレート、３－（パーフルオロ－３－メチルブチル）－２－ヒドロキシプロピル（メタ）アクリレート、３－（パーフルオロ－５－メチルヘキシル）－２－ヒドロキシプロピル（メタ）アクリレート、及び３－（パーフルオロ－７－メチルオクチル）－２－ヒドロキシプロピル（メタ）アクリレート等が挙げられる。 Examples of the monomer B include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluorobutyl) ethyl (meth). Acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ) Ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (Meth) acrylate, 1H, 1H, 5H-octafluorope Tyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) Acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluoro Octyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) Acrylate, and 3- (perfluoro-7-methyl-octyl) -2-hydroxypropyl (meth) acrylate.
　本発明において、前記モノマーＡと前記モノマーＢを共重合させる割合は、反応性や表面改質効果の観点から、好ましくは前記モノマーＡのモル数に対して前記モノマーＢ　５～３００モル％、より好ましくは１０～１５０モル％であり、さらに好ましくは２０～１００モル％である。 In the present invention, the ratio of copolymerizing the monomer A and the monomer B is preferably 5 to 300 mol% of the monomer B with respect to the number of moles of the monomer A, from the viewpoint of reactivity and surface modification effect. The amount is preferably 10 to 150 mol%, more preferably 20 to 100 mol%.
＜重合開始剤Ｃ＞
　前記重合開始剤Ｃとしては、好ましくはアゾ系重合開始剤が用いられる。アゾ系重合開始剤としては、例えば、以下の（１）～（６）に示す化合物を挙げられる。
（１）アゾニトリル化合物：
２，２'－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）、２，２'－アゾビス（２，４－ジメチルバレロニトリル）、１，１'－アゾビス（１－シクロヘキサンカルボニトリル）、２，２'－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２－（カルバモイルアゾ）イソブチロニトリル等；
（２）アゾアミド化合物：
２，２'－アゾビス｛２－メチル－Ｎ－［１，１－ビス（ヒドロキシメチル）－２－ヒドロキシエチル］プロピオンアミド｝、２，２'－アゾビス｛２－メチル－Ｎ－［２－（１－ヒドロキシブチル）］プロピオンアミド｝、２，２'－アゾビス［２－メチル－Ｎ－（２－ヒドロキシエチル）プロピオンアミド］、２，２'－アゾビス［Ｎ－（２－プロペニル）－２－メチルプロピオンアミド］、２，２'－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミド）、２，２'－アゾビス（Ｎ－シクロヘキシル－２－メチルプロピオンアミド）等；
（３）環状アゾアミジン化合物：
２，２'－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］ジヒドロクロリド、２，２'－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］ジスルフェートジヒドレート、２，２'－アゾビス[２－［１－（２－ヒドロキシエチル）－２－イミダゾリン－２－イル］プロパン]ジヒドロクロリド、２，２'－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］、２，２'－アゾビス（１－イミノ－１－ピロリジノ－２－メチルプロパン）ジヒドロクロリド等；
（４）アゾアミジン化合物：
２，２'－アゾビス（２－メチルプロピオンアミジン）ジヒドロクロリド、２，２'－アゾビス［Ｎ－（２－カルボキシエチル）－２－メチルプロピオンアミジン］テトラヒドレート等；
（５）その他：
２，２'－アゾビスイソ酪酸ジメチル、４，４'－アゾビス（４－シアノバレリン酸）、２，２'－アゾビス（２，４，４－トリメチルペンタン）、１，１'－アゾビス（１－アセトキシ－１－フェニルエタン）、ジメチル１，１'－アゾビス（１－シクロヘキサンカルボキシレート）、４，４'－アゾビス（４－シアノペンタン酸）；
（６）フルオロアルキル基含有アゾ系重合開始剤：
４，４'－アゾビス（４－シアノペンタン酸２－（パーフルオロメチル）エチル）、４，４'－アゾビス（４－シアノペンタン酸２－（パーフルオロブチル）エチル）、４，４'－アゾビス（４－シアノペンタン酸２－（パーフルオロヘキシル）エチル）等。 <Polymerization initiator C>
As the polymerization initiator C, an azo polymerization initiator is preferably used. Examples of the azo polymerization initiator include compounds shown in the following (1) to (6).
(1) Azonitrile compound:
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis ( 1-cyclohexanecarbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile and the like;
(2) Azoamide compound:
2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- ( 1-hydroxybutyl)] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [N- (2-propenyl) -2- Methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) and the like;
(3) Cyclic azoamidine compound:
2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) Propane], 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, etc .;
(4) Azoamidine compound:
2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, etc .;
(5) Other:
Dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2,4,4-trimethylpentane), 1,1′-azobis (1-acetoxy- 1-phenylethane), dimethyl 1,1′-azobis (1-cyclohexanecarboxylate), 4,4′-azobis (4-cyanopentanoic acid);
(6) Fluoroalkyl group-containing azo polymerization initiator:
4,4′-azobis (2-cyanopentanoic acid 2- (perfluoromethyl) ethyl), 4,4′-azobis (4-cyanopentanoic acid 2- (perfluorobutyl) ethyl), 4,4′-azobis (2-cyanopentanoic acid 2- (perfluorohexyl) ethyl) and the like.
　前記アゾ系重合開始剤の中でも、得られる含フッ素高分岐ポリマーの表面エネルギーの観点から、極性の比較的低い置換基を有するものが望ましく、特に２，２'－アゾビスイソ酪酸ジメチル又は２，２'－アゾビス（２，４，４－トリメチルペンタン）が好ましい。 Among the azo polymerization initiators, those having a substituent having a relatively low polarity are preferable from the viewpoint of the surface energy of the resulting fluorine-containing highly branched polymer, and in particular, dimethyl 2,2′-azobisisobutyrate or 2,2 ′ -Azobis (2,4,4-trimethylpentane) is preferred.
　前記重合開始剤Ｃは、前記モノマーＡのモル数に対して、５～２００モル％の量で使用され、好ましくは１５～２００モル％、より好ましくは１５～１７０モル％、最も好ましくは２０～１００モル％の量で使用される。 The polymerization initiator C is used in an amount of 5 to 200 mol%, preferably 15 to 200 mol%, more preferably 15 to 170 mol%, and most preferably 20 to 20 mol%, based on the number of moles of the monomer A. Used in an amount of 100 mol%.
＜含フッ素高分岐ポリマーの製造方法＞
　前記含フッ素高分岐ポリマーは、上記モノマーＡと上記モノマーＢとを、該モノマーＡ対して所定量の重合開始剤Ｃの存在下で重合させることで得られ、該重合方法としては公知の方法、例えば、溶液重合、分散重合、沈殿重合、及び塊状重合等が挙げられ、なかでも溶液重合又は沈殿重合が好ましい。特に分子量制御の点から、有機溶媒中での溶液重合によって反応を実施することが好ましい。
　このとき用いられる有機溶媒としては、ベンゼン、トルエン、キシレン、エチルベンゼン、テトラリン等の芳香族炭化水素系溶媒；ｎ－ヘキサン、ｎ－ヘプタン、ミネラルスピリット、シクロヘキサン等の脂肪族又は脂環式炭化水素系溶媒；塩化メチル、臭化メチル、ヨウ化メチル、メチレンジクロライド、クロロホルム、四塩化炭素、トリクロロエチレン、パークロロエチレン、オルトジクロロベンゼン等のハロゲン系溶媒；酢酸エチル、酢酸ブチル、メトキシブチルアセテート、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル系又はエステルエーテル系溶媒；ジエチルエーテル、テトラヒドロフラン、１，４－ジオキサン、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のエーテル系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン、ジ－ｎ－ブチルケトン、シクロヘキサノン等のケトン系溶媒；メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、ｔｅｒｔ－ブタノール、２－エチルヘキシルアルコール、ベンジルアルコール等のアルコール系溶媒；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系溶媒；ジメチルスルホキシド等のスルホキシド系溶媒；Ｎ－メチル－２－ピロリドン等の複素環式化合物系溶媒、並びにこれらの２種以上の混合溶媒が挙げられる。
　これらのうち好ましいのは、芳香族炭化水素系溶媒、ハロゲン系溶媒、エステル系又はエステルエーテル系溶媒、エーテル系溶媒、ケトン系溶媒、アルコール系溶媒、アミド系溶媒、スルホキシド系溶媒等であり、特に好ましいものはトルエン、キシレン、オルトジクロロベンゼン、酢酸ブチル、プロピレングリコールモノメ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、１，４－ジオキサン、メチルセロソルブ、メチルイソブチルケトン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等である。 <Method for producing fluorine-containing highly branched polymer>
The fluorine-containing hyperbranched polymer is obtained by polymerizing the monomer A and the monomer B in the presence of a predetermined amount of a polymerization initiator C with respect to the monomer A. For example, solution polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization and the like can be mentioned, and among these, solution polymerization or precipitation polymerization is preferable. In particular, it is preferable to carry out the reaction by solution polymerization in an organic solvent from the viewpoint of molecular weight control.
Examples of organic solvents used here include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane Solvent: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and other ester-based or ester ether-based solvents; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cello Ether solvents such as rub, butyl cellosolve, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, iso Alcohol solvents such as butanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol; amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; N-methyl- Examples include heterocyclic compound solvents such as 2-pyrrolidone, and mixed solvents of two or more of these.
Among these, preferred are aromatic hydrocarbon solvents, halogen solvents, ester solvents or ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, etc. Preferred are toluene, xylene, orthodichlorobenzene, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 1,4-dioxane, methyl cellosolve, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethyl Acetamide and the like.
　上記重合反応を有機溶媒の存在下で行う場合、重合反応物全体における有機溶媒の含量は、上記モノマーＡの１質量部に対し、好ましくは１～１００質量部、さらに好ましくは５～５０質量部である。
　重合反応は常圧、加圧密閉下、又は減圧下で行われ、装置及び操作の簡便さから常圧下で行うのが好ましい。また、Ｎ2等の不活性ガス雰囲気下で行うのが好ましい。
　重合反応の温度は、好ましくは５０～２００℃、さらに好ましくは７０～１５０℃である。
　より好ましくは、重合反応の温度は上記重合開始剤Ｃの１０時間半減期温度より２０℃以上高い温度で実施され、より具体的には、上記モノマーＡ、上記モノマーＢ、上記重合開始剤Ｃ及び有機溶媒を含む溶液を、該重合開始剤Ｃの１０時間半減期温度より２０℃以上高い温度に保たれた該有機溶媒中へ滴下することにより、重合反応を行うことが好ましい。
　また、さらにより好ましくは反応圧力下での前記有機溶媒の還流温度で重合反応を実施することが好ましい。
　重合反応の終了後、得られた含フッ素高分岐ポリマーを任意の方法で回収し、必要に応じて洗浄等の後処理を行う。反応溶液から高分子を回収する方法としては、再沈殿等の方法が挙げられる。 When the polymerization reaction is performed in the presence of an organic solvent, the content of the organic solvent in the entire polymerization reaction product is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 1 part by weight of the monomer A. It is.
The polymerization reaction is carried out under normal pressure, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Further, preferably carried out in an atmosphere of inert gas such as N 2.
The temperature of the polymerization reaction is preferably 50 to 200 ° C, more preferably 70 to 150 ° C.
More preferably, the temperature of the polymerization reaction is carried out at a temperature 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator C, and more specifically, the monomer A, the monomer B, the polymerization initiator C and The polymerization reaction is preferably carried out by dropping a solution containing the organic solvent into the organic solvent maintained at a temperature 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator C.
It is even more preferable to carry out the polymerization reaction at the reflux temperature of the organic solvent under a reaction pressure.
After completion of the polymerization reaction, the obtained fluorine-containing hyperbranched polymer is collected by an arbitrary method, and post-treatment such as washing is performed as necessary. Examples of a method for recovering the polymer from the reaction solution include a method such as reprecipitation.
　得られた含フッ素高分岐ポリマーの重量平均分子量（以下、Ｍｗと略記）は、ゲル浸透クロマトグラフィー（ＧＰＣ）によるポリスチレン換算で好ましくは１，０００～２００，０００、さらに好ましくは２，０００～１００，０００、最も好ましくは５，０００～６０，０００である。 The weight average molecular weight (hereinafter abbreviated as Mw) of the obtained fluorine-containing highly branched polymer is preferably 1,000 to 200,000, more preferably 2,000 to 100, in terms of polystyrene by gel permeation chromatography (GPC). 5,000, most preferably 5,000 to 60,000.
［熱可塑性樹脂］
　前記熱可塑性樹脂としては特に限定されないが、例えばＰＥ（ポリエチレン）、ＰＰ（ポリプロピレン）、ＥＶＡ（エチレン－酢酸ビニル共重合体）、ＥＥＡ（エチレン－アクリル酸エチル共重合体）などのポリオレフィン系樹脂；ＰＳ（ポリスチレン）、ＨＩＰＳ（ハイインパクトポリスチレン）、ＡＳ（アクリロニトリル－スチレン共重合体）、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン共重合体）、ＭＳ（メタクリル酸メチル－スチレン共重合体）などのポリスチレン系樹脂；ポリカーボネート樹脂；塩化ビニル樹脂；ポリアミド樹脂；ポリイミド樹脂；ＰＭＭＡ（ポリメチルメタクリレート）などの（メタ）アクリル樹脂；ＰＥＴ（ポリエチレンテレフタレート）、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ＰＬＡ（ポリ乳酸）、ポリ－３－ヒドロキシ酪酸、ポリカプロラクトン、ポリブチレンサクシネート、ポリエチレンサクシネート／アジペートなどのポリエステル樹脂；ポリフェニレンエーテル樹脂；変性ポリフェニレンエーテル樹脂；ポリアセタール樹脂；ポリスルホン樹脂；ポリフェニレンサルファイド樹脂；ポリビニルアルコール樹脂；ポリグルコール酸；変性でんぷん；酢酸セルロース、三酢酸セルロース；キチン、キトサン；リグニン等が挙げられる。
　なかでもポリメチルメタクリレート樹脂又はポリ乳酸樹脂が好ましい。 [Thermoplastic resin]
The thermoplastic resin is not particularly limited. For example, a polyolefin resin such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); Polystyrene resins such as PS (polystyrene), HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer) Polycarbonate resin; polyamide resin; polyimide resin; (meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate Polybutylene naphthalate, PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate / adipate and other polyester resins; polyphenylene ether resins; modified polyphenylene ether resins; polyacetal resins; polysulfone resins Polyphenylene sulfide resin; polyvinyl alcohol resin; polyglycolic acid; modified starch; cellulose acetate, cellulose triacetate; chitin, chitosan; lignin and the like.
Of these, polymethyl methacrylate resin or polylactic acid resin is preferable.
［樹脂組成物］
　前記樹脂組成物において、前記（ｂ）熱可塑性樹脂１００質量部に対して（ａ）含フッ素高分岐ポリマーの配合量は、好ましくは０．０１～２０質量部であり、より好ましくは０．１～２０質量部であり、さらに好ましくは０．１～１０質量部である。 [Resin composition]
In the resin composition, the amount of the (a) fluorine-containing highly branched polymer is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 100 parts by mass of the (b) thermoplastic resin. To 20 parts by mass, and more preferably 0.1 to 10 parts by mass.
　前記樹脂組成物には、熱可塑性樹脂と共に一般に添加される添加剤、例えば、帯電防止剤、滑剤、熱安定剤、酸化防止剤、光安定剤、蛍光剤、加工助剤、架橋剤、分散剤、発泡剤、難燃剤、消泡剤、補強剤、顔料などを併用してもよい。 Additives generally added to the resin composition together with the thermoplastic resin, such as antistatic agents, lubricants, thermal stabilizers, antioxidants, light stabilizers, fluorescent agents, processing aids, crosslinking agents, dispersants , Foaming agents, flame retardants, antifoaming agents, reinforcing agents, pigments, and the like may be used in combination.
［押出成形フィルム］
　本発明の押出成形フィルムは、上記（ａ）含フッ素高分岐ポリマー及び（ｂ）熱可塑性樹脂を配合して溶融混練し、場合によってはその他の所望の成分も配合して溶融混練し、そして公知の押出成形法により得ることができる。 [Extruded film]
The extruded film of the present invention is blended with the above-mentioned (a) fluorine-containing hyperbranched polymer and (b) thermoplastic resin and melt-kneaded. In some cases, other desired components are blended and melt-kneaded. Can be obtained by the extrusion molding method.
　前記押出成形フィルムの厚さは特に限定されないが、通常０．０１～２．０ｍｍ、好ましくは０．０１～１．５ｍｍであり、より好ましくは０．０１～１．０ｍｍである。 The thickness of the extruded film is not particularly limited, but is usually 0.01 to 2.0 mm, preferably 0.01 to 1.5 mm, and more preferably 0.01 to 1.0 mm.
　本発明の押出成形フィルムは、前述の通り、フィルムの内部（深部）に比べて、フィルムの表面（界面）部に上記含フッ素高分岐ポリマーが多く存在した状態にある。このため、本発明の押出成形フィルムは、フィルム等の他の樹脂フィルムに対する剥離性、さらには撥水・撥油性及び透明性に優れたフィルムとなる。 As described above, the extruded film of the present invention is in a state in which more of the fluorine-containing highly branched polymer is present on the surface (interface) portion of the film than in the inside (deep portion) of the film. For this reason, the extrusion-molded film of the present invention is a film excellent in peelability from other resin films such as a film, and further in water / oil repellency and transparency.
　以下、実施例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。
　なお、実施例において、試料の調製及び物性の分析に用いた装置及び条件は、以下の通りである。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.
（１）ゲル浸透クロマトグラフィー（ＧＰＣ）
　装置：東ソー（株）製　ＨＬＣ－８２２０ＧＰＣ
　カラム：Ｓｈｏｄｅｘ（登録商標）　ＫＦ－８０４Ｌ、ＫＦ－８０５Ｌ
　カラム温度：４０℃
　溶媒：テトラヒドロフラン
　検出器：ＲＩ
（２）1Ｈ　ＮＭＲスペクトル及び13Ｃ　ＮＭＲスペクトル
　装置：日本電子データム（株）製　ＪＮＭ－ＥＣＡ７００
　溶媒：ＣＤＣｌ3
　内部標準：テトラメチルシラン
（３）イオンクロマトグラフィー（Ｆ定量分析）
　装置：日本ダイオネクス（株）製　ＩＣＳ－１５００
　溶媒：（２．７ｍｍｏｌ Ｎａ2ＣＯ3　＋　０．３ｍｍｏｌ ＮａＨＣＯ3）／Ｌ水溶液
　検出器：電気伝導度
（４）スピンコーター
　装置：ミカサ（株）製　ＭＳ－Ａ１００
（５）エリプソメトリー（屈折率及び膜厚測定）
　装置：Ｊ．Ａ．Ｗｏｏｌｌａｍ社製　ＥＣ－４００
（６）接触角測定
　装置：ＡＳＴ　Ｐｒｏｄｕｃｔｓ社製　ＶＣＡ　Ｏｐｔｉｍａ
　測定温度：２０℃
（７）ガラス転移温度（Ｔｇ）測定
　装置：ＰｅｒｋｉｎＥｌｍｅｒ社製　Ｄｉａｍｏｎｄ　ＤＳＣ
　測定条件：窒素雰囲気下
　昇温速度：５℃／分（２５～１６０℃）
（８）５％重量減少時温度（Ｔｄ5%）測定
　装置：（株）リガク製　ＴＧ８１２０
　測定条件：空気雰囲気下
　昇温速度：１０℃／分（２５～５００℃）
（９）簡易混練機
　装置：（株）東洋精機製作所製　ラボプラストミル
（１０）二軸混練押出機
　装置：（株）テクノベル製　ＫＺＷ－１５ＴＷ（Ｌ／Ｄ＝４５）
（１１）ヘイズメーター（濁度測定）
　装置：日本電色工業（株）製　ＮＤＨ５０００ (1) Gel permeation chromatography (GPC)
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex (registered trademark) KF-804L, KF-805L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: RI
(2) 1 H NMR spectrum and 13 C NMR spectrum Apparatus: JNM-ECA700 manufactured by JEOL Datum Co., Ltd.
Solvent: CDCl 3
Internal standard: Tetramethylsilane (3) ion chromatography (F quantitative analysis)
Equipment: ICS-1500 manufactured by Nippon Dionex Co., Ltd.
Solvent: (2.7 mmol Na 2 CO 3 + 0.3 mmol NaHCO 3 ) / L aqueous solution Detector: Electrical conductivity (4) Spin coater Device: MS-A100 manufactured by Mikasa Corporation
(5) Ellipsometry (refractive index and film thickness measurement)
Apparatus: J.M. A. EC-400 manufactured by Woollam
(6) Contact angle measurement device: VCA Optima manufactured by AST Products
Measurement temperature: 20 ° C
(7) Glass transition temperature (Tg) measurement Device: Diamond DSC manufactured by PerkinElmer
Measurement conditions: Under nitrogen atmosphere Temperature rising rate: 5 ° C / min (25 to 160 ° C)
(8) 5% weight loss temperature (Td 5% ) measurement device: TG8120 manufactured by Rigaku Corporation
Measurement conditions: In air atmosphere Temperature rising rate: 10 ° C / min (25-500 ° C)
(9) Simple kneader Equipment: Labo Plast Mill, manufactured by Toyo Seiki Seisakusho Co., Ltd. (10) Twin-screw kneading extruder Equipment: KZW-15TW, manufactured by Technobel Co., Ltd. (L / D = 45)
(11) Haze meter (turbidity measurement)
Device: NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
　また、略記号は以下の意味を表す。
ＥＧＤＭＡ：エチレングリコールジメタクリレート［新中村化学工業（株）製　１Ｇ］
Ｃ６ＦＡ：２－（パーフルオロヘキシル）エチルアクリレート［ユニマテック（株）製　ＦＡＡＣ－６］
ＭＡＩＢ：２，２’－アゾビスイソ酪酸ジメチル［大塚化学（株）製　ＭＡＩＢ］
ＭＭＡ：メチルメタクリレート［和光純薬工業（株）製］
ＰＭＭＡ：ポリメチルメタクリレート［クラレ（株）製　パラペットＧ（ＭＦＲ＝８．０ｇ／１０分）］
ＴＨＦ：テトラヒドロフラン
ＭＥＫ：メチルエチルケトン
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート Abbreviations represent the following meanings.
EGDMA: Ethylene glycol dimethacrylate [1G made by Shin-Nakamura Chemical Co., Ltd.]
C6FA: 2- (perfluorohexyl) ethyl acrylate [FAAC-6 manufactured by Unimatec Co., Ltd.]
MAIB: Dimethyl 2,2′-azobisisobutyrate [MAIB manufactured by Otsuka Chemical Co., Ltd.]
MMA: Methyl methacrylate [Wako Pure Chemical Industries, Ltd.]
PMMA: Polymethyl methacrylate [Kuraray Co., Ltd. Parapet G (MFR = 8.0 g / 10 min)]
THF: Tetrahydrofuran MEK: Methyl ethyl ketone PGMEA: Propylene glycol monomethyl ether acetate
［合成例１］高分岐ポリマー１の合成
　２００ｍＬの反応フラスコに、トルエン３２ｇを仕込み、撹拌しながら５分間窒素を流し込み、内液が還流するまで（およそ温度１１０℃）加熱した。
　別の１００ｍＬの反応フラスコに、ＥＧＤＭＡ　４．０ｇ（２０ｍｍｏｌ）、Ｃ６ＦＡ　４．２ｇ（１０ｍｍｏｌ）、ＭＡＩＢ　２．３ｇ（１０ｍｍｏｌ）及びトルエン３２ｇを仕込み、撹拌しながら５分間窒素を流し込むことにより窒素置換を行い、氷浴にて０℃まで冷却を行った。
　前述の２００ｍＬの反応フラスコ中の還流してあるトルエン中に、ＥＧＤＭＡ、Ｃ６ＦＡ及びＭＡＩＢが仕込まれた前記１００ｍＬの反応フラスコから、滴下ポンプを用いて、内容物を３０分間かけて滴下した。滴下終了後、１時間熟成させた。
　次に、この反応液をヘキサン／トルエン（質量比４：１）２７７ｇに添加してポリマーをスラリー状態で沈殿させた。このスラリーを減圧濾過し、ＴＨＦ　３６ｇを用いて再溶解し、このポリマーのＴＨＦ溶液をヘキサン２７７ｇに添加してポリマーをスラリー状態で再沈殿させた。このスラリーを減圧濾過し、真空乾燥して、白色粉末の目的物（高分岐ポリマー１）４．９ｇを得た（収率４８％）。
　得られた目的物の1Ｈ　ＮＭＲ及び13Ｃ　ＮＭＲスペクトルを図１及び図２に示す。また、目的物のＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは１７，０００、分散度：Ｍｗ（重量平均分子量）／Ｍｎ（数平均分子量）は２．２であった。 [Synthesis Example 1] Synthesis of hyperbranched polymer 1 A 200 mL reaction flask was charged with 32 g of toluene, and nitrogen was introduced for 5 minutes while stirring, and the mixture was heated until the internal solution was refluxed (approximately 110 ° C.).
Into another 100 mL reaction flask, EGDMA 4.0 g (20 mmol), C6FA 4.2 g (10 mmol), MAIB 2.3 g (10 mmol) and toluene 32 g were charged, and nitrogen substitution was performed by flowing nitrogen for 5 minutes while stirring. And cooled to 0 ° C. in an ice bath.
The contents were added dropwise from the 100 mL reaction flask charged with EGDMA, C6FA and MAIB to the refluxed toluene in the 200 mL reaction flask using a dropping pump over 30 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, this reaction liquid was added to 277 g of hexane / toluene (mass ratio 4: 1) to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure, redissolved using 36 g of THF, and a THF solution of this polymer was added to 277 g of hexane to reprecipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 4.9 g of the target product (highly branched polymer 1) as a white powder (yield 48%).
1 H NMR and 13 C NMR spectra of the obtained target product are shown in FIGS. 1 and 2. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 17,000, and dispersion degree: Mw (weight average molecular weight) / Mn (number average molecular weight) was 2.2.
［合成例２］高分岐ポリマー２の合成
　２００ｍＬの反応フラスコに、トルエン４４ｇを仕込み、撹拌しながら５分間窒素を流し込み、内液が還流するまで（およそ温度１１０℃）加熱した。
　別の１００ｍＬの反応フラスコに、ＥＧＤＭＡ　４．０ｇ（２０ｍｍｏｌ）、Ｃ６ＦＡ　４．２ｇ（１０ｍｍｏｌ）、ＭＡＩＢ　２．８ｇ（１２ｍｍｏｌ）及びトルエン４４ｇを仕込み、撹拌しながら５分間窒素を流し込むことにより窒素置換を行い、氷浴にて０℃まで冷却を行った。
　前述の２００ｍＬの反応フラスコ中の還流してあるトルエン中に、ＥＧＤＭＡ、Ｃ６ＦＡ及びＭＡＩＢが仕込まれた前記１００ｍＬの反応フラスコから、滴下ポンプを用いて、内容物を３０分間かけて滴下した。滴下終了後、１時間熟成させた。
　次に、この反応液からロータリーエバポレーターを用いてトルエン７５ｇを留去後、ヘキサン２７８ｇに添加してポリマーをスラリー状態で沈殿させた。このスラリーを減圧濾過し、真空乾燥して、白色粉末の目的物（高分岐ポリマー２）４．４ｇを得た（収率４３％）。
　得られた目的物の1Ｈ　ＮＭＲ及び13Ｃ　ＮＭＲスペクトルを図３及び図４に示す。また、目的物のＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは６，８００、分散度：Ｍｗ／Ｍｎは１．９であった。 [Synthesis Example 2] Synthesis of Hyperbranched Polymer 2 To a 200 mL reaction flask, 44 g of toluene was charged, nitrogen was poured for 5 minutes with stirring, and the mixture was heated until the internal liquid was refluxed (approximately 110 ° C.).
In another 100 mL reaction flask, EGDMA 4.0 g (20 mmol), C6FA 4.2 g (10 mmol), MAIB 2.8 g (12 mmol) and toluene 44 g were charged, and nitrogen substitution was performed by flowing nitrogen for 5 minutes with stirring. And cooled to 0 ° C. in an ice bath.
The contents were added dropwise from the 100 mL reaction flask charged with EGDMA, C6FA and MAIB to the refluxed toluene in the 200 mL reaction flask using a dropping pump over 30 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, 75 g of toluene was distilled off from this reaction solution using a rotary evaporator, and then added to 278 g of hexane to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and vacuum dried to obtain 4.4 g of the target product (highly branched polymer 2) as a white powder (43% yield).
The 1 H NMR and 13 C NMR spectra of the obtained target product are shown in FIGS. 3 and 4. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 6,800, and dispersion degree: Mw / Mn was 1.9.
［合成例３］直鎖状ポリマー１の合成
　１００ｍＬの反応フラスコに、ＭＭＡ　８．０ｇ（８０ｍｍｏｌ）、Ｃ６ＦＡ　８．４ｇ（２０ｍｍｏｌ）、ＭＡＩＢ　０．９２ｇ（４ｍｍｏｌ）及びＭＥＫ　２７ｇを仕込み、撹拌しながら５分間窒素を流し込むことにより窒素置換を行った後、液温８０℃で７時間撹拌した。
　次に、この反応液をヘキサン６６２ｇに添加してポリマーを沈殿させ、上澄み液をデカンテーションした。残った沈殿物を、ＴＨＦ　５４ｇを用いて再溶解し、このポリマーのＴＨＦ溶液をヘキサン６６２ｇに添加してポリマーをスラリー状態で再沈殿させた。このスラリーを減圧濾過し、真空乾燥して、白色粉末の目的物（直鎖状ポリマー１）６．６ｇを得た（収率４０％）。
　得られた目的物の1Ｈ　ＮＭＲ及び13Ｃ　ＮＭＲスペクトルを図５及び図６に示す。また、目的物のＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは２１，０００、分散度：Ｍｗ／Ｍｎは２．０であった。 Synthesis Example 3 Synthesis of Linear Polymer 1 MMA 8.0 g (80 mmol), C6FA 8.4 g (20 mmol), MAIB 0.92 g (4 mmol) and MEK 27 g were charged into a 100 mL reaction flask while stirring. After carrying out nitrogen substitution by flowing nitrogen for 5 minutes, the mixture was stirred at a liquid temperature of 80 ° C. for 7 hours.
Next, this reaction solution was added to 662 g of hexane to precipitate a polymer, and the supernatant was decanted. The remaining precipitate was redissolved using 54 g of THF, and a THF solution of this polymer was added to 662 g of hexane to reprecipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 6.6 g of the target product (linear polymer 1) as a white powder (yield 40%).
1 H NMR and 13 C NMR spectra of the obtained target product are shown in FIGS. 5 and 6. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 21,000, and dispersion degree: Mw / Mn was 2.0.
　合成例１～３で得られた高分岐ポリマー１及び２並びに直鎖状ポリマー１の重量平均分子量Ｍｗ、分散度：Ｍｗ／Ｍｎ、13Ｃ　ＮＭＲからのフッ素モノマー導入量、フッ素定量分析からのフッ素原子含有量を表１に示す。 Weight average molecular weight Mw, dispersity: Mw / Mn, amount of fluorine monomer introduced from 13 C NMR, fluorine from quantitative fluorine analysis of hyperbranched polymers 1 and 2 and linear polymer 1 obtained in Synthesis Examples 1 to 3 The atomic content is shown in Table 1.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
［参考例１］各ポリマーの物性評価
　合成例１～３で得られた高分岐ポリマー１及び２並びに直鎖状ポリマー１の各０．２５ｇを、表２に記載の溶媒４．７５ｇに溶解させてフィルタろ過を行い、各高分岐ポリマー溶液又は直鎖状ポリマー溶液を調製した。この高分岐ポリマー溶液又は直鎖状ポリマー溶液をシリコンウェハー上にスピンコーティング（ｓｌｏｐｅ５秒間、次いで２，０００ｒｐｍ３０秒間、さらにｓｌｏｐｅ５秒間）し、１００℃にて３０分間の熱処理を行うことにより溶媒を蒸発させて、成膜した。
　得られた薄膜の波長６３３ｎｍにおける屈折率、並びに水及びジヨードメタンの接触角の評価を行った。また接触角の結果から表面エネルギーを算出した。さらに、各高分岐ポリマー粉末又は直鎖状ポリマー粉末のガラス転移温度（Ｔｇ）及び５％重量減少温度（Ｔｄ5%）を測定した。得られた結果を表２に示す。 [Reference Example 1] Evaluation of physical properties of each polymer 0.25 g of each of the hyperbranched polymers 1 and 2 and the linear polymer 1 obtained in Synthesis Examples 1 to 3 was dissolved in 4.75 g of the solvent described in Table 2. Filter filtration was performed to prepare each hyperbranched polymer solution or linear polymer solution. The hyperbranched polymer solution or linear polymer solution is spin-coated on a silicon wafer (slope 5 seconds, then 2,000 rpm for 30 seconds, then slope 5 seconds), and the solvent is evaporated by performing a heat treatment at 100 ° C. for 30 minutes. A film was formed.
The refractive index of the obtained thin film at a wavelength of 633 nm and the contact angles of water and diiodomethane were evaluated. The surface energy was calculated from the result of the contact angle. Further, the glass transition temperature (Tg) and 5% weight loss temperature (Td 5% ) of each hyperbranched polymer powder or linear polymer powder were measured. The obtained results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
［実施例１］高分岐ポリマー添加ＰＭＭＡマスターバッチの作製
　高分岐ポリマー１又は高分岐ポリマー２　１０ｇと、ＰＭＭＡ４０ｇとを、簡易混練機を用いて温度２３０℃、回転数５０ｒｐｍで５分間混練し、高分岐ポリマー濃度２０質量％のＰＭＭＡマスターバッチを作製した。 [Example 1] Production of hyperbranched polymer-added PMMA masterbatch 10 g of hyperbranched polymer 1 or hyperbranched polymer 2 and 40 g of PMMA were kneaded at a temperature of 230 ° C and a rotation speed of 50 rpm for 5 minutes using a simple kneader. A PMMA master batch having a branched polymer concentration of 20% by mass was prepared.
［実施例２～１９］高分岐ポリマー添加ＰＭＭＡ押出成形フィルムの作製
　二軸混練押出機に、高分岐ポリマー含有ＰＭＭＡ中の高分岐ポリマー濃度が表３に示す濃度になるように、実施例１で作製したマスターバッチ及びＰＭＭＡを投入し、スクリュー回転数１００ｒｐｍ、吐出量２ｇ／分、ダイ幅２０ｍｍ、ダイリップ間隔０．８ｍｍ、及びそれぞれ表３に示す条件で押出成形フィルムを作製した。
　得られたフィルムの水及びヘキサデカンの接触角の評価を行った。得られた結果を、表３に合わせて示す。 [Examples 2 to 19] Production of highly branched polymer-added PMMA extruded film In Example 1, the highly branched polymer concentration in the highly branched polymer-containing PMMA was adjusted to the concentration shown in Table 3 in a twin-screw kneading extruder. The prepared master batch and PMMA were added, and an extrusion-molded film was prepared under the conditions shown in Table 3 for a screw rotation speed of 100 rpm, a discharge rate of 2 g / min, a die width of 20 mm, and a die lip interval of 0.8 mm.
The contact angle of water and hexadecane of the obtained film was evaluated. The obtained results are shown in Table 3 together.
［比較例１］直鎖状ポリマー添加ＰＭＭＡマスターバッチの作製
　実施例１と同様にして、直鎖状ポリマー濃度２０質量％のＰＭＭＡマスターバッチを作製した。 [Comparative Example 1] Production of linear polymer-added PMMA masterbatch A PMMA masterbatch having a linear polymer concentration of 20% by mass was produced in the same manner as in Example 1.
［比較例２～６］直鎖状ポリマー添加ＰＭＭＡ押出成形フィルムの作製
　高分岐ポリマーに替えて直鎖状ポリマーを使用した以外は実施例２と同様に操作し、押出成形フィルムを作製した。
　得られたフィルムの水及びヘキサデカンの接触角の評価を行った。得られた結果を、表３に合わせて示す。 [Comparative Examples 2 to 6] Production of linear polymer-added PMMA extruded film An extruded film was produced in the same manner as in Example 2 except that a linear polymer was used instead of the highly branched polymer.
The contact angle of water and hexadecane of the obtained film was evaluated. The obtained results are shown in Table 3 together.
［比較例７］ＰＭＭＡ押出成形フィルムの作製
　高分岐ポリマーを添加しなかった以外は実施例２と同様に操作し、押出成形フィルムを作製した。
　得られたフィルムの水及びヘキサデカンの接触角の評価を行った。得られた結果を、表３に合わせて示す。 Comparative Example 7 Production of PMMA Extruded Film An extruded film was produced in the same manner as in Example 2 except that the hyperbranched polymer was not added.
The contact angle of water and hexadecane of the obtained film was evaluated. The obtained results are shown in Table 3 together.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表３に示す通り、高分岐ポリマーを添加したＰＭＭＡフィルム（実施例２～１９）は、水の接触角が８１．５～１０１．９度、ヘキサデカンの接触角が３５．２～５７．０度といずれも高い接触角を示した。この結果から、ＰＭＭＡ押出成形フィルムに高分岐ポリマーを添加することで、ＰＭＭＡ押出成形フィルムに撥液性が付与されたことが明らかとなった。 As shown in Table 3, the PMMA films (Examples 2 to 19) to which the hyperbranched polymer was added had a water contact angle of 81.5 to 101.9 degrees and a hexadecane contact angle of 35.2 to 57.0 degrees. Both showed high contact angles. From this result, it was revealed that liquid repellency was imparted to the PMMA extruded film by adding a hyperbranched polymer to the PMMA extruded film.
［ＰＭＭＡ押出成形フィルムの透明性評価］
　実施例２，９，１１，１３，１５～１８、及び比較例２～５，７で作製した各押出成形フィルムの濁度（ｈａｚｅ値）を測定し、以下の基準により透明性を評価した。得られた結果を表４に示す。
［濁度の評価基準］
　○：　　　ｈａｚｅ値＜１０
　△：１０≦ｈａｚｅ値＜５０
　×：５０≦ｈａｚｅ値 [Transparency evaluation of PMMA extruded film]
The turbidity (haze value) of each of the extruded films produced in Examples 2, 9, 11, 13, 15 to 18 and Comparative Examples 2 to 5 and 7 was measured, and the transparency was evaluated according to the following criteria. Table 4 shows the obtained results.
[Evaluation criteria for turbidity]
○: haze value <10
Δ: 10 ≦ haze value <50
×: 50 ≦ haze value
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　表４に示す通り、直鎖状ポリマー添加ＰＭＭＡ押出成形フィルム（比較例２～５）は、透明性が低かった。これに対し、高分岐ポリマー添加ＰＭＭＡ押出成形フィルム（実施例１３～１８）は、透明性が優れていた。この結果から、ＰＭＭＡ押出成形フィルムに高分岐ポリマーを添加しても、ＰＭＭＡ押出成形フィルム本来の透明性が損なわれないことが明らかとなった。 As shown in Table 4, the linear polymer-added PMMA extruded film (Comparative Examples 2 to 5) had low transparency. In contrast, the highly branched polymer-added PMMA extruded films (Examples 13 to 18) were excellent in transparency. From this result, it became clear that even if a highly branched polymer was added to the PMMA extruded film, the original transparency of the PMMA extruded film was not impaired.

Claims (15)

  1. （ａ）分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にフルオロアルキル基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＢとを、該モノマーＡのモル数に対して、５～２００モル％の量の重合開始剤Ｃの存在下で重合させることにより得られる含フッ素高分岐ポリマー、及び（ｂ）熱可塑性樹脂、を含む樹脂組成物を押出成形することによって得られる表面改質された押出成形フィルム。 (A) a monomer A having two or more radically polymerizable double bonds in the molecule, and a monomer B having a fluoroalkyl group and at least one radically polymerizable double bond in the molecule; Extrusion molding of a resin composition comprising a fluorine-containing highly branched polymer obtained by polymerization in the presence of a polymerization initiator C in an amount of 5 to 200 mol% relative to the number of moles, and (b) a thermoplastic resin A surface-modified extruded film obtained by
  2. 前記モノマーＡがビニル基又は（メタ）アクリル基の何れか一方を少なくとも１つ有する化合物である、請求項１に記載の押出成形フィルム。 The extruded film according to claim 1, wherein the monomer A is a compound having at least one of a vinyl group and a (meth) acryl group.
  3. 前記モノマーＡがジビニル化合物又はジ（メタ）アクリレート化合物である、請求項２に記載の押出成形フィルム。 The extruded film according to claim 2, wherein the monomer A is a divinyl compound or a di (meth) acrylate compound.
  4. 前記モノマーＡがエチレングリコールジ（メタ）アクリレートである、請求項３に記載の押出成形フィルム。 The extruded film according to claim 3, wherein the monomer A is ethylene glycol di (meth) acrylate.
  5. 前記モノマーＡのモル数に対して５～３００モル％の量の前記モノマーＢを用いて得られる、請求項１に記載の押出成形フィルム。 The extruded film according to claim 1, obtained by using the monomer B in an amount of 5 to 300 mol% based on the number of moles of the monomer A.
  6. 前記モノマーＢがビニル基又は（メタ）アクリル基の何れか一方を少なくとも１つ有する化合物である、請求項５に記載の押出成形フィルム。 The extrusion-molded film according to claim 5, wherein the monomer B is a compound having at least one of either a vinyl group or a (meth) acryl group.
  7. 前記モノマーＢが下記式［１］で表される化合物である、請求項６に記載の押出成形フィルム。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数２～１２のフルオロアルキル基を表す。）     The extrusion film of Claim 6 whose said monomer B is a compound represented by following formula [1].
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a fluoroalkyl group having 2 to 12 carbon atoms.)
  8. 前記モノマーＢが下記式［２］で表される化合物である、請求項７に記載の押出成形フィルム。
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ1は前記式［１］における定義と同じ意味を表し、Ｘは水素原子又はフッ素原子を表し、ｍは１又は２を表し、ｎは０～５の整数を表す。）     The extrusion film of Claim 7 whose said monomer B is a compound represented by following formula [2].
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, R 1 has the same meaning as defined in the formula [1], X represents a hydrogen atom or a fluorine atom, m represents 1 or 2, and n represents an integer of 0 to 5.)
  9. 前記重合開始剤Ｃがアゾ系重合開始剤である、請求項１乃至請求項８のうち何れか一項に記載の押出成形フィルム。 The extruded film according to any one of claims 1 to 8, wherein the polymerization initiator C is an azo polymerization initiator.
  10. 前記重合開始剤Ｃが２，２'－アゾビスイソ酪酸ジメチルである、請求項９に記載の押出成形フィルム。 The extruded film according to claim 9, wherein the polymerization initiator C is dimethyl 2,2'-azobisisobutyrate.
  11. 前記（ａ）含フッ素高分岐ポリマーの含有量が、前記（ｂ）熱可塑性樹脂１００質量部に対して０．０１乃至２０質量部である、請求項１乃至請求項１０のうち何れか一項に記載の押出成形フィルム。 The content of the (a) fluorine-containing highly branched polymer is 0.01 to 20 parts by mass with respect to 100 parts by mass of the (b) thermoplastic resin. An extruded film according to 1.
  12. 前記（ｂ）熱可塑性樹脂がポリメチルメタクリレートである、請求項１乃至請求項１１のうち何れか一項に記載の押出成形フィルム。 The extruded film according to any one of claims 1 to 11, wherein the (b) thermoplastic resin is polymethyl methacrylate.
  13. フィルムの内部に比べて、該フィルムの表面部において前記（ａ）含フッ素高分岐ポリマーの含有割合がより高いことを特徴とする、請求項１乃至請求項１２のうち何れか一項に記載の押出成形フィルム。 The content ratio of the (a) fluorine-containing highly branched polymer is higher in the surface portion of the film than in the inside of the film, according to any one of claims 1 to 12. Extruded film.
  14. フィルムの厚さが０．０１～２．０ｍｍである、請求項１乃至請求項１３のうち何れか一項に記載の押出成形フィルム。 The extruded film according to any one of claims 1 to 13, wherein the film has a thickness of 0.01 to 2.0 mm.
  15. （ａ）分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にフルオロアルキル基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＢとを、該モノマーＡのモル数に対して、５～２００モル％の量の重合開始剤Ｃの存在下で重合させることにより得られる含フッ素高分岐ポリマー、及び（ｂ）熱可塑性樹脂、を含む樹脂組成物を押出成形することを特徴とする、表面改質された押出成形フィルムの製造方法。 (A) a monomer A having two or more radically polymerizable double bonds in the molecule, and a monomer B having a fluoroalkyl group and at least one radically polymerizable double bond in the molecule; Extrusion molding of a resin composition comprising a fluorine-containing highly branched polymer obtained by polymerization in the presence of a polymerization initiator C in an amount of 5 to 200 mol% relative to the number of moles, and (b) a thermoplastic resin A method for producing a surface-modified extruded film, characterized by comprising:
PCT/JP2011/077805 2010-12-01 2011-12-01 Surface-modified extrusion-molded film WO2012074055A1 (en)

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