WO2021014836A1 - Modificateur de résine fluorée, et corps moulé de résine fluorée modifié ainsi que procédé de fabrication de celui-ci - Google Patents

Modificateur de résine fluorée, et corps moulé de résine fluorée modifié ainsi que procédé de fabrication de celui-ci Download PDF

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WO2021014836A1
WO2021014836A1 PCT/JP2020/023694 JP2020023694W WO2021014836A1 WO 2021014836 A1 WO2021014836 A1 WO 2021014836A1 JP 2020023694 W JP2020023694 W JP 2020023694W WO 2021014836 A1 WO2021014836 A1 WO 2021014836A1
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fluororesin
molded product
group
block copolymer
structural unit
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PCT/JP2020/023694
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Japanese (ja)
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八尾　滋
翔 平井
涼子 中野
優太 牛島
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学校法人福岡大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a fluororesin modifier.
  • the present invention also relates to a modified fluororesin molded product and a method for producing the same.
  • Fluororesin such as polytetrafluoroethylene (PTFE), which is a polymer of tetrafluoroethylene, is excellent in chemical stability, heat resistance, solvent resistance, weather resistance, electrical insulation, etc., and therefore in various fields. It's being used. On the other hand, the surface of the fluororesin is inert, and there are problems such as poor adhesion to other materials. Therefore, various modification methods are being studied in order to expand the use of the fluororesin.
  • PTFE polytetrafluoroethylene
  • Patent Document 1 As a method for modifying fluororesin, physical treatment such as plasma or laser, or a method combining this with chemical treatment is known.
  • Patent Document 1 when plasma irradiation is performed on the surface of a fluororesin-based molded product, ions in the plasma are injected into the surface of the molded product to roughen the surface by applying a negative voltage to the surface of the molded product.
  • a method for surface modification of a fluororesin-based molded article is disclosed, which involves physical modification and chemical modification in which a fluororesin atom on the surface of the molded article is replaced with an atom other than the fluorine atom.
  • Patent Document 2 describes a step (1) of introducing an active point into the surface of a fluororesin-based molded product by irradiating the surface of the fluororesin-based molded product with plasma, and an atmospheric gas that requires a water-soluble monomer having an unsaturated bond.
  • the present inventors are copolymers having a structural unit derived from the first monomer (A) and a structural unit derived from the second monomer (B), and the monomer ( A) is selected from the group consisting of (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, ⁇ -olefin and substituted styrene having a fluorinated alkyl group represented by a specific structural formula in its side chain.
  • Disclosed is a method for modifying a fluororesin using a copolymer in which the monomer (B) is a monomer having a functional group.
  • Patent Documents 1 and 2 the method of introducing an active site on the surface of a fluororesin by plasma treatment and causing a chemical reaction at this active site is a complicated shape in which only the portion irradiated with plasma is surface-modified. There was a problem that it was not suitable for modifying the molded product of.
  • one of the partial structures is a linear or branched perfluoro.
  • Various regulations are being studied for substances having a heptyl group ((C 7 F 15 ) C-) that can be decomposed to emit PFOA. Therefore, there is a concern that the design of a monomer having an alkyl fluorinated group in the side chain is limited.
  • an object of the present invention is to provide a new fluororesin modifier that can be used for modifying a fluororesin.
  • Another object of the present invention is to provide a modified fluororesin molded product to which various desired functionalitys are imparted and a method for producing the same.
  • the present invention relates to the following invention.
  • the fluororesin modifier according to ⁇ 1> or ⁇ 2> which is a block copolymer solution containing the block copolymer and a solvent.
  • the fluororesin modifier is brought into contact with the fluororesin polymer, and has a surface modification step of forming a functional layer containing the fluororesin modifier on at least a part of the surface of the fluororesin polymer.
  • a method for producing a modified fluororesin molded product which contains a copolymer. ⁇ 5> The method for producing a modified fluororesin molded product according to ⁇ 4>, which comprises a roughening step of roughening the surface of the fluororesin molded product before the surface modification step.
  • a modified fluororesin molded product having a fluororesin molded product and a functional layer containing a block copolymer formed on at least a part of the surface of the fluororesin molded product, wherein the block copolymer is formed.
  • a modified fluororesin molded product which is a block copolymer containing a structural unit (A) derived from the above and a structural unit (B) derived from the monomer (B) having a polar group.
  • a method for modifying a fluororesin polymer in which the fluororesin modifier is brought into contact with the fluororesin polymer, and the fluororesin modifier is applied to at least a part of the surface of the fluororesin polymer.
  • a new fluororesin modifier that can be used for modifying a fluororesin molded product is provided. Further, according to the present invention, there is provided a modified fluororesin molded product to which various desired functionalitys are imparted, and a method for producing the same. For example, according to the present invention, there is provided a modified fluororesin molded product having excellent adhesiveness to other materials and a method for producing the same.
  • the present invention is any monomer selected from the group consisting of (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, ⁇ -olefin and substituted styrene having an alkyl group having 8 or more carbon atoms in the side chain.
  • a fluororesin modifier containing a block copolymer containing a structural unit (A) derived from A) and a structural unit (B) derived from a monomer (B) having a polar group hereinafter, “the present invention”. It may be described as "fluororesin modifier").
  • a modifier that chemically modifies fluororesin has a reactive functionality that allows radical reaction with fluororesin.
  • the present inventors have a structural unit (A) derived from a monomer (A) having an alkyl group having 8 or more carbon atoms in a side chain, which has a structure different from that of a fluororesin, and a monomer (B) having a polar group.
  • a block copolymer containing the structural unit (B) derived from the above can surprisingly adhere to the surface of the fluororesin. Furthermore, by using such a block copolymer, it is possible to impart functionality derived from the structural unit (B) to the fluororesin, and in particular, it is possible to modify the fluororesin to one having excellent adhesiveness to other materials. I found it.
  • the polymer having a long-chain alkyl fluoride group is concerned about the limitation of the structure that can be used from the environmental point of view.
  • the block copolymer used in the present invention has a low environmental load and a high degree of freedom in design, and it is easy to appropriately change the design according to the structure of the fluororesin to be modified.
  • the block copolymer contained in the fluororesin modifier of the present invention contains (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, ⁇ -olefin and ⁇ -olefin having an alkyl group having 8 or more carbon atoms in the side chain. It is a block copolymer containing a structural unit (A) derived from any of the monomers (A) selected from the group consisting of substituted styrene and a structural unit (B) derived from the monomer (B) having a polar group. ..
  • the block copolymer may be composed of a structural unit (A) and a structural unit (B), and may further contain other structural units as long as the object of the present invention is not impaired.
  • the block copolymer is preferably composed substantially of the structural unit (A) and the structural unit (B), and in the block copolymer, the total of the structural unit (A) and the structural unit (B).
  • the content of the above can be 95% by mass or more, 98% by mass or more, and the like.
  • the structural unit (A) is any monomer selected from the group consisting of (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, ⁇ -olefin and substituted styrene having an alkyl group having 8 or more carbon atoms. It is derived from A).
  • the structural unit (A) becomes a site that exhibits side chain crystallinity by having an alkyl group having 8 or more carbon atoms, and the block copolymer can be formed by interacting with the fluororesin with the portion that exhibits side chain crystallinity. It is presumed that it adheres firmly to the fluororesin.
  • (meth) acrylate means both acrylate and methacrylate.
  • (meth) acrylamide means both acrylamide and metaacrylamide.
  • the alkyl group having a length of 8 or more carbon atoms in the side chain is directly bonded or linked to the main chain of the structural unit (A) (ester bond, amide bond, ether bond, benzene ring, etc.). It is connected via.
  • the alkyl group having a length of 8 or more carbon atoms in the side chain is preferably an alkyl group having 12 or more carbon atoms because the fluororesin and the block copolymer can be more firmly bonded to each other. More preferably, 16 or more alkyl groups. Further, the alkyl group is preferably a linear alkyl group.
  • the upper limit thereof can be appropriately set within a range in which the adhesiveness between the block copolymer and the fluororesin can be maintained in consideration of dispersibility in a solvent and the like. As a specific upper limit, in reality, the number of carbon atoms is 50 or less, more preferably 40 or less, and further preferably 30 or less.
  • the number of carbon atoms may be 28 or less or 25 or less. If the number of carbon atoms in the alkyl group is too large, an appropriate three-dimensional structure cannot be obtained as a block copolymer, and the adhesiveness of the block copolymer to the fluororesin is lowered or the dispersibility in the solvent is lowered. In addition, it may be difficult to set the polymerization conditions for producing a block copolymer.
  • examples of the alkyl group having 8 or more carbon atoms in the side chain of the structural unit (A) include a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group (stearyl group), and a docosyl group.
  • examples include a group (behenyl group).
  • the degree of polymerization of the structural unit (A) is 2 or more.
  • the degree of polymerization of the structural unit (A) may be appropriately selected within a range in which the adhesiveness to the fluororesin can be maintained, depending on the structure of the monomer (A) and the monomer (B) and the like.
  • the degree of polymerization of the structural unit (A) is preferably 7 or more, and may be 8 or more or 10 or more.
  • the degree of polymerization of the structural unit (A) is preferably 1,000 or less, and may be 800 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.
  • the molecular weight (g / mol) corresponding to the structural unit (A) is preferably 3,000 or more.
  • the molecular weight corresponding to the structural unit (A) may be 4,000 or more or 5,000 or more. Further, it may be 20,000 or less, 15,000 or less, 10,000 or less, or 8,000 or less.
  • molecular weights are values "Mw: weight average molecular weight” that can be obtained in terms of polystyrene from the results obtained by GPC.
  • the modifying copolymer may be difficult to dissolve in a solvent and it may be difficult to measure the molecular weight.
  • the molecular weight of each can be calculated by a method such as elemental analysis, IR, or NMR.
  • the structural unit (A) is preferably a structural unit derived from a (meth) acrylate or ⁇ -olefin monomer having an alkyl group having a length of 8 or more carbon atoms in the side chain. More specifically, the structural unit (A) is preferably any of the following general formulas (A-1) or (A-2).
  • Ra1 represents a hydrogen atom or a methyl group.
  • Ra2 represents an alkyl group having 8 or more carbon atoms. As described above, Ra2 is preferably a linear alkyl group.
  • the alkyl group represented by R a2 preferably has 12 or more carbon atoms, and more preferably 16 or more carbon atoms. Further, the upper limit can be 50 or less, 40 or less, 30 or less, 28 or less, 25 or less, and the like.
  • m is an integer of 2 or more.
  • the m is preferably 7 or more, preferably 8 or more, or 10 or more.
  • m is preferably 1,000 or less, and may be 800 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.
  • the structural unit (A) Is more preferably the general formula (A-1).
  • the structural unit (B) is a structural unit derived from the monomer (B) having a polar group. While the structural unit (A) exerts a function of adhering to the fluororesin, the structural unit (B) has a function of imparting the functionality to the fluororesin and modifying the fluororesin. For example, the structural unit (B) contributes to the improvement of adhesiveness with other materials.
  • a polar group is a group of polar atoms, which is present in a polymer using a monomer having that group to form a structure showing polarity in the polymer. Since the polar group is present in the polymerized body after the polymerization, it can be modified into a fluororesin having excellent adhesiveness to other materials due to the polarity imparted to the surface of the fluororesin.
  • the polar group may be present in the main chain structure of the structural unit (B) or in the side chain. Further, the structural unit (B) may have two or more polar groups. Since the polarity derived from the polar group of the structural unit (B) is likely to be expressed on the surface of the modified fluororesin and the modification effect is large, the structural unit (B) preferably has a polar group in its side chain. .. When the side chain has a polar group, the structure of the main chain is not particularly limited because the main chain has little effect on the modification of the fluororesin.
  • the polar group of the side chain may have a structure in which it is directly bonded to the main chain of the structural unit (B) or bonded via a linking group (ester bond, amide bond, ether bond, benzene ring, etc.).
  • the structural unit (B) is any monomer selected from the group consisting of (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, ⁇ -olefin and substituted styrene having a polar group in the side chain. It can be a structural unit derived from.
  • Typical polar groups include amino groups, ammonium groups, carboxyl groups, hydroxyl groups, sulfonic acid groups, alkoxy groups, oxyalkylene groups, carbonyl groups, ether groups, sulfonyl groups, ester groups, amide groups and the like.
  • the structural unit (B) preferably has any one selected from the group consisting of an amino group, a hydroxyl group and an oxyalkylene group. More preferably, the monomer (B) constituting the structural unit (B) is a monomer having any one selected from the group consisting of an amino group, a hydroxyl group and an oxyalkylene group in its side chain.
  • the amino group may be unsubstituted or have a substituent.
  • the transamination group is preferably a group represented by the general formula "-NR y3 R y4 (where R y3 and R y4 are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms)". .. Examples of such an amino group include -NH 2 , -N (CH 3 ) 2 , -N (C 2 H 5 ) 2 , and -NH (tert-C 4 H 9 ).
  • the oxyalkylene group is a divalent group represented by "-(C p H 2p -O)-" (p is an integer of 1 or more).
  • the monomer (B) has an oxyalkylene group, it is preferably a monomer having a group represented by the following general formula (X).
  • Equation (X) (In the formula (X), p is an integer of 1 to 10, q is an integer of 1 to 10, and R x1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
  • p is an integer of 1 to 5
  • q is an integer of 2 to 10
  • R x 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. More preferably, p is an integer of 1 to 2, q is an integer of 2 to 10, and R x 1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
  • the degree of polymerization of the structural unit (B) is an integer of 2 or more.
  • the degree of polymerization of the structural unit (B) is appropriately determined according to the structure of the monomer (A) and the monomer (B).
  • the degree of polymerization of the structural unit (B) is preferably 2 to 1,000. In order to exert a more stable reforming effect, it is more preferably 5 or more or 10 or more. Further, it may be 20 or more, 30 or more, and 40 or more.
  • the degree of polymerization of the structural unit (B) may be 800 or less, 500 or less, 300 or less, 100 or less, or 60 or less.
  • the molecular weight (g / mol) corresponding to the structural unit (B) is preferably 500 or more.
  • the molecular weight corresponding to the structural unit (B) is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. Further, it may be 20,000 or less, 15,000 or less, or 12,000 or less.
  • the structural unit (B) can have, for example, the structures of the following general formulas (B-1) to (B-4).
  • R b1 represents a hydrogen atom or a methyl group.
  • RL represents a single bond or an alkylene group, and is preferably a single bond or an alkylene group having 1 to 4 carbon atoms.
  • R b2 is represented by a hydrogen atom, an alkyl group, an amino group, an ammonium group, a carboxyl group, a hydroxyl group, a sulfonic acid group, an alkoxy group and the above general formula (X).
  • R b2 is preferably any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an amino group and a group represented by the above general formula (X), and is preferably a hydrogen atom and an amino group. It is more preferable that it is selected from the group consisting of the groups represented by the general formula (X), and it is further preferable that it is an amino group.
  • the preferred amino group and the mode of the group represented by the general formula (X) are as described above.
  • R b3 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • n is an integer of 2 or more. n is preferably 8 or more, and may be 10 or more, 20 or more, 30 or more, or 40 or more. Further, n is preferably 1,000 or less, and may be 800 or less, 500 or less, 300 or less, 100 or less, or 60 or less.
  • structural unit (B) can have the structures of the following general formulas (B-5) to (B-7).
  • R b4 represents a hydrogen atom or a methyl group.
  • RL represents a single bond or an alkylene group, and is preferably a single bond or an alkylene group having 1 to 4 carbon atoms.
  • R b5 is a group consisting of an amino group, an ammonium group, a carboxyl group, a hydroxyl group, a sulfonic acid group, an alkoxy group and a group represented by the general formula (X). Represents one selected from. R b5 is preferably an amino group or a group represented by the above general formula (X), and more preferably an amino group. The preferred amino group and the mode of the group represented by the general formula (X) are as described above.
  • n is an integer of 2 or more. n may be 5 or more, 10 or more, 20 or more, 30 or more, 40 or more. Further, n is preferably 1,000 or less, and may be 800 or less, 500 or less, 300 or less, 100 or less, or 60 or less.
  • the structural unit (B) is preferably a general formula (B-1) from the viewpoint of easy availability of a monomer as a raw material and easy control of polymerization conditions.
  • R b1 is a hydrogen atom or a methyl group
  • RL is an alkylene group
  • R b2 is an amino group.
  • R b1 is a hydrogen atom or a methyl group
  • RL is a single bond
  • R b2 is a group represented by the general formula (X).
  • a structural unit derived from (meth) acrylic acid in the general formula (B-1), R b1 is a hydrogen or a methyl group, RL is a single bond, and R b2 is a hydrogen atom).
  • One of the preferred block copolymers is a copolymer containing a structural unit (A) represented by the general formula (A-1) and a structural unit (B) represented by the general formula (B-1). is there.
  • A structural unit represented by the general formula (A-1)
  • B structural unit represented by the general formula (B-1).
  • the method of polymerizing the block copolymer is not particularly limited, and it is possible to polymerize by a known technique such as various living polymerization methods (radicals, anions, cations).
  • a living radical polymerization method an NMP method, an ATRP method, a RAFT method and the like can be used.
  • a monomer (A) mixed solution preparation step is performed in which the monomer (A) is mixed with a polymerization solvent together with an initiator to prepare a monomer (A) mixed solution.
  • the monomer (A) mixed solution prepared in this mixed solution preparation step is appropriately stirred in a reactor at an appropriate polymerization temperature (for example, about 90 to 120 ° C.), and a living radical is subjected to a nitrogen atmosphere or the like.
  • a monomer (A) polymerization step based on the polymerization mechanism of the initiator such as polymerization is carried out to obtain a monomer (A) block polymer.
  • a monomer (B) polymerization step is performed in which the monomer (B) is mixed with the solution in which the monomer (A) block polymer is mixed, and the monomer (B) is further polymerized by radicals or the like in the solution.
  • a block copolymer having a block derived from the monomer (A) and a block derived from the monomer (B) can be obtained.
  • the order in which the monomer (A) and the monomer (B) are polymerized can be changed according to the type of monomer to be polymerized, the molecular weight, the polymerization conditions of each, and the like.
  • the monomer (A) is exemplified by dodecyl acrylate (lauryl acrylate), dodecyl methacrylate (lauryl methacrylate), octadecyl acrylate (stearyl acrylate), octadecyl methacrylate (stearyl methacrylate), docosyl acrylate (behenyl acrylate), and docosyl.
  • dodecyl acrylate (lauryl acrylate), dodecyl methacrylate (lauryl methacrylate), octadecyl acrylate (stearyl acrylate), octadecyl methacrylate (stearyl methacrylate), docosyl acrylate (behenyl acrylate), and docosyl.
  • dodecyl acrylate (lauryl acrylate)
  • dodecyl methacrylate (lauryl methacrylate)
  • the monomer (B) are 2- (Dimethylamino) ethyl Methacrylate, DMAEA, 2- (Dimethylamino) ethyl Acrylate, DMAEA. , 2- (Diethylamino) ethyl Methacrylate, DEAEMA, 2- (Diethylamino) ethyl Acrylate, DEAEA, 2- (tert-butylamino) ethyl methacrylate (2- (Diethylamino) ethyl Acrylate, DEAEA) 2- (tert-Butylamino) ethyl Methacrylate, TBAEMA), N, N-dimethylacrylamide (N, N-Dimethylacrylamide, DMAA), N, N-dimethylaminopropylacrylamide (N, N-Dimethylaminopropyl Acrylamide, DMAPAA), and N , N-diethylacrylamide (N, N-Diethylacrylamide (
  • Diethylen Glycol Monoethyl Ether Acrylate, DEEA Diethylen Glycol Monoethyl Ether Acrylate
  • (meth) acrylic acid and the like can be mentioned.
  • the fluororesin modifier of the present invention may contain other components other than the block copolymer.
  • the fluororesin modifier of the present invention can be a block copolymer solution containing a block copolymer and a solvent.
  • the desired properties such as adhesiveness can be imparted to a desired range of the fluororesin molded product by adjusting the viscosity and concentration to an arbitrary level. It will be easier to do.
  • the block copolymer solution is a concept that includes not only a uniform solution in which the block copolymer is completely dissolved in a solvent, but also a suspension / dispersion solution. Depending on the structure of the block copolymer, it may be difficult to completely dissolve the block copolymer in the solvent. Therefore, the block copolymer can be used as a suspension or a dispersion liquid in which the block copolymer is suspended or dispersed in the solvent. Good.
  • the solvent is not particularly limited, and examples thereof include toluene, xylene, hexane, butyl acetate, acetonitrile, ethanol, dimethyl sulfoxide, and tetrahydrofuran.
  • the solvent may be a single solvent composed of only one kind or a mixed solvent composed of two or more kinds of solvents.
  • it is a solvent containing at least one selected from the group consisting of toluene, butyl acetate, xylene and tetrahydrofuran.
  • the fluororesin modifier contains a mixed solvent
  • one or more selected from the group consisting of toluene, butyl acetate, xylene and tetrahydrofuran is used as the main solvent.
  • any one selected from the group consisting of toluene, butyl acetate, xylene and tetrahydrofuran preferably accounts for 50% by volume or more, and 70% by volume or more, 90% by volume or more, 95 by volume or more in the total volume of the solvent. It may occupy more than% by volume.
  • concentration of the block copolymer in the fluororesin modifier depends on the type of block copolymer, the method of using the fluororesin modifier, and the like. Can be set as appropriate.
  • the concentration of the block copolymer in the fluororesin modifier is preferably 0.01 to 2.0% by mass.
  • the lower limit of the concentration of the block copolymer is preferably 0.02% by mass or more, more preferably 0.05% by mass or more. If the concentration of the block copolymer is too low, the modifying effect on the fluororesin may be insufficient.
  • the upper limit of the concentration of the block copolymer is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. It can be 0.8% by mass or less, 0.6% by mass or less, or 0.5% by mass or less. Even if the concentration of the block copolymer is increased, the modifying effect on the fluororesin may be saturated. Further, if the concentration of the block copolymer is too high, micelle formation due to self-assembly of the block copolymer itself may occur, and the block copolymer may not sufficiently function as a modifier for fluororesin.
  • the fluororesin modifier of the present invention is a method for modifying a fluororesin molded product, in which the fluororesin modifier is brought into contact with the fluororesin molded product, and the fluororesin is applied to at least a part of the surface of the fluororesin molded product.
  • the fluororesin modifier of the present invention is brought into contact with the fluororesin molded product to form a functional layer containing the fluororesin modifier on at least a part of the surface of the fluororesin molded product.
  • the present invention relates to a method for producing a modified fluororesin molded product, which is subjected to a quality step (hereinafter, may be referred to as “a method for producing a modified fluororesin molded product of the present invention”).
  • the method for producing a modified fluororesin molded product of the present invention is a method for obtaining a modified fluororesin molded product by modifying the fluororesin molded product using the above-mentioned fluororesin modifier of the present invention.
  • the modified fluororesin molded product By manufacturing the modified fluororesin molded product by such a manufacturing method, the modified fluororesin obtained by easily imparting various desired functionality to the desired portion regardless of the shape of the fluororesin molded product and the like.
  • a molded product can be obtained.
  • the method for producing a fluororesin molded product of the present invention by adjusting the viscosity of the fluororesin modifier of the present invention, even a molded product having a complicated shape can be uniformly treated with the fluororesin modifier. Therefore, it can be modified regardless of its shape. Further, in a physical method such as plasma treatment, the molded body may be damaged and the mechanical strength may be lowered depending on the shape of the fluororesin molded body such as a thin film.
  • the method for producing the modified fluororesin molded product of the present invention is a chemical method, and even for a molded product in which damage or a decrease in mechanical strength is likely to occur due to a physical method, damage or mechanical strength of the molded product It can be modified by suppressing the decrease.
  • the inside of the porous material by the conventional modification method such as plasma treatment, but in the method for producing the modified fluororesin molded article of the present invention, the inside of the hole of the molded article or the like
  • the fluororesin modifier can be impregnated into the inside thereof to easily modify the entire porous material.
  • the fluororesin molded product used in the method for producing a modified fluororesin molded product of the present invention is a fluororesin molded into an arbitrary shape depending on the intended use or the like.
  • the fluororesin is not particularly limited, and a homopolymer of a monomer containing fluorine or a copolymer with another monomer can be used.
  • polytetrafluoroethylene tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride system (THV), polyvinylidene fluoride system (PVDF), polychlorotrifluoroethylene system (PCTFE), Examples thereof include chlorotrifluoroethylene-ethylene system (ECTFE), tetrafluoroethylene-ethylene system (ETFE), tetrafluoroethylene-hexafluoropropylene system (FEP), and tetrafluoroethylene-perfluoroalkyl vinyl ether system (PFA).
  • ECTFE chlorotrifluoroethylene-ethylene system
  • ETFE tetrafluoroethylene-ethylene system
  • FEP tetrafluoroethylene-hexafluoropropylene system
  • PFA tetrafluoroethylene-perfluoroalkyl vinyl ether system
  • the shape of the fluororesin molded product is not particularly limited, and examples thereof include molded products such as sheets, films, particles, plates, and porous materials.
  • the fluororesin modifier of the present invention is brought into contact with the fluororesin molded product to form a functional layer containing the fluororesin modifier on at least a part of the surface of the fluororesin molded product. It is a process.
  • the fluororesin modifier of the present invention used in the method for producing a modified fluororesin molded product of the present invention is as described above, and even if it is a block copolymer, a block containing a block copolymer and a solvent. It may contain components other than the block copolymer, such as a copolymer solution. From the viewpoint of the modifying effect of the obtained modified fluororesin molded product, it is preferable to use a block copolymer solution containing a block copolymer and a solvent as the fluororesin modifier of the present invention. By using a block copolymer solution, it is easy to adjust the viscosity to an arbitrary value, and the fluororesin molded product can be brought into more uniform contact.
  • the functionality can be more uniformly imparted to the desired portion of the obtained modified fluororesin molded product, and the imparted functionality tends to be improved as a whole.
  • it is easy to more uniformly and overall improve the adhesiveness to other materials at a desired portion of the obtained modified fluororesin molded product.
  • the degree of freedom of the block copolymer at the time of contact with the fluororesin molded product is improved, it is easy for the block copolymer to have a structure in which it easily interacts with the fluororesin molded product, and the block copolymer and the fluororesin molded product can be molded. It can work more strongly with the body.
  • the structural unit (B) of the block copolymer is easily present on the outermost surface of the fluororesin molded product, the functionality imparted to the surface of the modified fluororesin molded product (for example, with other materials). Adhesiveness) will be better. In addition, it becomes easy to control the thickness of the functional layer formed on the fluororesin molded product.
  • the method of contacting the fluororesin modifier of the present invention with the fluororesin molded product is particularly provided if a functional layer containing the fluororesin modifier of the present invention can be formed on at least a part of the surface of the fluororesin molded product.
  • contact methods include dipping such as dip coating, coating (coating) such as spin coating, applicator coating, slit coating, die coating, bar coating, screen printing, inkjet printing, and gravure printing, and spraying such as spray coating. Be done.
  • the contact between the copolymer solution and the fluororesin molded product may be any method as long as the copolymer solution can be brought into contact with the portion of the fluororesin molded product to be modified, and the shape or modification of the fluororesin molded product may be used. It may be appropriately selected according to the range to be quality and the like.
  • the treatment temperature when the fluororesin modifier and the fluororesin molded product are brought into contact with each other is appropriately determined according to the contact method, the composition of the fluororesin modifier, the type of the fluororesin molded product, and the like. Just do it.
  • the treatment temperature may be room temperature, and may be carried out under temperature conditions higher than room temperature in consideration of safety and the like.
  • the processing temperature can be 20 ° C. or higher or 25 ° C. or higher.
  • the fluororesin molded product may be deformed or decomposed, so the upper limit thereof can be set to 200 ° C. or lower or 150 ° C. or lower.
  • the fluororesin modifier or fluororesin molded product is heated to a preset temperature according to the contact method or the like, and then the fluororesin modifier and fluororesin are used.
  • the molded product may be brought into contact with the molded product, or the fluororesin modifier and the fluororesin molded product may be brought into contact with each other and then heated to a set temperature.
  • the treatment time for contacting the fluororesin modifier and the fluororesin molded product can be appropriately determined according to the composition of the fluororesin modifier, the type of the fluororesin molded product, and the like.
  • the treatment time may be relatively short, such as 1 second or more or 30 seconds or more.
  • the processing time may be 1 minute or more or 5 minutes or more.
  • the treatment time may be long, and may be 60 minutes or less or 40 minutes or less. Further, since the reforming effect is saturated when the contact time exceeds a certain time, it may be 30 minutes or less or 20 minutes or less depending on the conditions such as the treatment temperature.
  • the amount of the fluororesin modifier applied is not particularly limited as long as it can be uniformly applied to the portion of the fluororesin molded product to be modified.
  • the coating amount can be 10 to 300 g / m 2 , 50 to 250 g / m 2 , 100 to 250 g / m 2 , and the like.
  • a solvent for removing the solvent after the surface modification step is usually performed.
  • a functional layer is formed.
  • a method for removing the solvent it may be dried at around room temperature in a well-ventilated environment, or may be appropriately subjected to vacuum drying, heat drying, or the like. Moreover, you may use these drying methods together.
  • fluororesin molding is performed before the surface modification step within a range that does not significantly impair the mechanical strength of the fluororesin molded product according to the shape of the fluororesin molded product and the like. It may have a step of roughening the surface of the body.
  • the roughening step is a step carried out before the surface modification step, and is a step of roughening the surface of the fluororesin molded product.
  • the roughening method is not particularly limited, and conventionally known methods such as sanding, blasting, and etching can be used.
  • the degree of roughening may be appropriately determined in consideration of the mechanical properties and purpose of the obtained fluororesin molded product according to the roughening method, the shape of the fluororesin molded product, and the like.
  • the surface of the fluororesin molded product can be roughened so that the maximum height roughness (Rz) is 80 ⁇ m or less or 60 ⁇ m or less.
  • the lower limit of the maximum height roughness (Rz) of the surface of the fluororesin molded product can be 10 ⁇ m or more or 20 ⁇ m or more. Further, the surface of the fluororesin molded product can be roughened so that the arithmetic mean roughness (Ra) is 15 ⁇ m or less, 10 ⁇ m or less, and 8 ⁇ m or less.
  • the lower limit of the arithmetic mean roughness (Ra) of the surface of the fluororesin molded product can be set to 1 ⁇ m or more or 3 ⁇ m or more.
  • the maximum height roughness (Rz) and the arithmetic mean roughness (Ra) of the surface are surface roughness defined by JIS B 0633 (2001).
  • the present invention is a modified fluororesin molded product having a fluororesin molded product and a functional layer containing a block copolymer formed on at least a part of the surface of the fluororesin molded product.
  • the copolymer is selected from the group consisting of (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, ⁇ -olefin and substituted styrene having an alkyl group having 8 or more carbon atoms in the side chain.
  • a modified fluororesin molded product (hereinafter, "", which is a block copolymer containing a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B) having a polar group. It may be described as "modified fluororesin polymer of the present invention”).
  • the modified fluororesin molded product of the present invention can be suitably produced by the method for producing the modified fluororesin molded product of the present invention, and the block co-weight contained in the functional layer of the modified fluororesin molded product of the present invention.
  • the coalescence has the same structure as the block copolymer contained in the fluororesin modifier of the present invention.
  • the preferred embodiment of the block copolymer is the same as described above.
  • the formation of the functional layer on the surface of the fluororesin molded product can be confirmed by a method such as component analysis of each layer by FT-IR or the like, or component analysis of the cut surface.
  • the structure may have a structure having a functional layer containing a block copolymer on at least a part of the surface of the modified fluororesin molded product, and the functional layer is formed in a desired range of the fluororesin molded product depending on the purpose. It suffices if it is done.
  • the entire surface layer of the sheet-shaped or particle-shaped molded product may have a functional layer, or the surface layer may have a mottled or striped functional layer.
  • the structure may have a functional layer in the pores of a porous membrane or the like.
  • the functional layer may be a layer made of a block copolymer or may contain other components different from the block copolymer.
  • the functional layer contains a block copolymer as a main component.
  • the content of the block copolymer in the functional layer can be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and the like.
  • the shape of the fluororesin molded product is not particularly limited, and examples thereof include molded products such as sheets, particles, plates, porous materials, and various members.
  • Block Copolymer (1-1) Production of Copolymer (BHA-TBAEMA) 5.0 g of butyl acetate and 5.0 g of behenyl acrylate (BHA) are placed in a separable flask to obtain butyl acetate. After mixing BHA, deaeration and nitrogen substitution were performed. The mixture of butyl acetate and BHA was stirred under a nitrogen atmosphere, BHA was dissolved in butyl acetate, and then 0.38 g of an initiator (Blocbuilder MA) was added. BHA was polymerized at 110 ° C. for 24 hours in a nitrogen atmosphere to obtain a solution of the BHA polymer.
  • BHA-TBAEMA behenyl acrylate
  • BHA-TBAEMA 2- (tert-butylamino) ethyl methacrylate
  • BHA-TBAEMA 2- (tert-butylamino) ethyl methacrylate
  • STA-DEEA block copolymer of STA and DEEA
  • Acrylic acid (AA) 3.42 g and butyl acetate 3.42 g were added to a solution of the STA polymer, and polymerization was further carried out at 105 ° C. for 27 hours under a nitrogen atmosphere. Methanol was added and reprecipitation was performed to obtain a block copolymer of STA and AA (STA-AA).
  • Mw weight average molecular weight
  • Block copolymer solution fluororesin modifier
  • block copolymer solution (1) BHA-TBAEMA is used as the block copolymer, and tetrahydrofuran (THF) is used as the solvent. Using. BHA-TBAEMA was added to THF and mixed so that the concentration of the block copolymer was 0.1 wt%, and 100 g of the block copolymer solution (1) was prepared.
  • Block Copolymers (2) to (11) Block Coweight except that the amounts of block copolymer, solvent, and block copolymer added are changed so as to have the composition shown in Table 1.
  • Block copolymer solutions (2) to (11) were prepared in the same manner as in the coalesced solution (1).
  • PTFE film Film (F1-a) A 100 ⁇ m-thick PTFE film (manufactured by Sampler Tech) was cut into a size of 12.5 ⁇ 0.5 mm ⁇ 100 mm to obtain a film (F1-a).
  • Film (F1-b) A PTFE film (manufactured by Sampler Tech) having a thickness of 500 ⁇ m was cut into a size of 12.5 ⁇ 0.5 mm ⁇ 100 mm to obtain a film (F1-b).
  • Film (F2-b) A 500 ⁇ m-thick PTFE film (manufactured by Sampler Tech) was cut into a size of 130 mm ⁇ 200 mm to obtain a film (F2-b).
  • Example 1 Production (immersion) of a modified fluororesin molded product (Example 1-1)
  • the block copolymer solution (1) 100 g was placed in a separable flask, and the temperature was raised to 60 ° C. (modification temperature) in an oil bath. When the temperature reached 60 ° C., 10 films (F1-a) were hung with a wire and immersed. After 10 minutes, all films were removed from the block copolymer solution (1).
  • the film after treatment with the block copolymer solution (1) was vacuum-dried (45 ° C., 30 min) to obtain 10 modified films (A1).
  • Example 2 Modified films (A2) to (A13) were obtained in the same manner as in Example 1-1 except that the block copolymer solution and the modification temperature were changed as shown in Table 2.
  • test piece for T-type peeling test was prepared in accordance with JIS K6854-3 (1999). Using 10 modified films obtained under the same production conditions, 5 test pieces under the same production conditions were produced. First, two modified films were adhered using Aron Alpha. Then, it was dried at 100 ° C. for 20 minutes to obtain a test piece. For comparison, a test piece obtained by similarly adhering unmodified films (F1-a) to each other with Aron Alpha was obtained.
  • T-type peeling test A T-type peeling test was performed in accordance with K6854-3 (1999) using the five test pieces prepared, and the average value of the maximum test force and the average test force of the five test pieces was calculated. Calculated. The results are shown in Table 2.
  • modified films A1 to A13 are excellent in the average test force and the maximum test force with respect to the unmodified film (F1-a), and the adhesiveness is improved.
  • Example 2 Production (coating) of a modified fluororesin molded product
  • the short side (130 mm side) of the film (F2-a) was arranged horizontally and the long side (200 mm side) was vertically arranged on the glass plate of the tabletop coater.
  • the slit width (distance between the glass plate and the applicator) was set to 1.1 mm so that the distance between the applicator and the film for stretching the solution was 1 mm.
  • the block copolymer solution (6) about 3 mL
  • the block copolymer solution (6) is stretched at a coating rate of 10 mm / min, and the block copolymer solution (6) is stretched onto the film (F2-a).
  • the film (F2-a) coated with the block copolymer solution (6) was vacuum-dried (45 ° C., 30 min) to obtain a modified film (b1).
  • the obtained modified film (b1) was cut into a size of 12.5 ⁇ 0.5 mm ⁇ 100 mm to obtain a total of 10 modified films (B1).
  • Example 3 Production of modified fluororesin molded product (spray) (Example 3-1)
  • the block copolymer solution (6) was filled in a spray container, and the block copolymer solution was sprayed on the surface of the film (F1-a).
  • the film (F1-a) sprayed with the block copolymer solution (6) was vacuum-dried (45 ° C., 30 min) to obtain a modified film (C1).
  • the same operation was carried out to obtain a total of 10 modified films (C1).
  • the amount of the block copolymer solution used to produce 10 modified films was about 3 mL.
  • Example 3-2 The same as in Example 3-1 except that the block copolymer solution (3) was used instead of the block copolymer solution (6) and the film (F2-a) was used instead of the film (F1-a). 10 sheets of modified film (C2) were obtained.
  • the modified film modified by coating or spraying the block copolymer solution also has improved adhesiveness.
  • Example 4 Production of modified fluororesin molded product (production method having a roughening step) (Example 4-1)
  • the film (F1-b) was roughened by polishing the film surface five times in substantially the same direction using sandpaper No. 180 to obtain a film (f1-b). The same operation was performed to prepare 10 films (f1-b).
  • the degree of roughening of this film (f1-b) was determined by using a 3D measurement laser microscope OLS4100 (manufactured by SIMADZU) (cutoff wavelength: 80 ⁇ m, objective lens: MPLFLLN10x, image size: 1280 ⁇ 1280 ⁇ m) and JIS B 0663 ( When measured according to 2001), the maximum height roughness (Rz) was 43 ⁇ m, and the arithmetic mean roughness (Ra) was 6.5 ⁇ m. Then, the same operation as in Example 1-5 was carried out except that the film (f1-b) was used instead of the film (F1-a), and 10 modified films (A5-R) were obtained.
  • Example 4-2 The film (F2-b) was roughened by polishing the film surface 5 times in substantially the same direction using sandpaper No. 180 to obtain a film (f2-b).
  • the same operation as in Example 2 was performed except that the film (f2-b) was used instead of the film (F2-a) and the slit width (distance between the glass plate and the applicator) was set to 1.5 mm. This was carried out to obtain 10 modified films (B1-R) (12.5 ⁇ 0.5 mm ⁇ 100 mm).
  • Example 4-3 Ten films (f1-b) were prepared in the same manner as in Example 4-1. Next, the same operation as in Example 3-1 was performed except that the film (f1-b) was used instead of the film (F1-a), and 10 modified films (C1-R) were obtained.
  • Example 4-4 to 4-6 Ten films (f1-b) were prepared in the same manner as in Example 4-1. Next, Example 3-1 except that the film (f1-b) was used instead of the film (F1-a) and the block copolymer solution shown in Table 4 was used instead of the block copolymer solution (6). The same operation as in the above was carried out to obtain 10 modified films (C2-R) to (C4-R), respectively.
  • the block copolymer (BHA-TBAEMA) in the fluororesin modifier of the present invention is modified. Although it does not have a structure similar to that of the target PTFE, it has the same or higher adhesive strength as when treated with a block copolymer solution (DFHA-TBAEMA) that has a structure similar to that of the target PTFE. It turns out that it can be granted.
  • the fluororesin modifier of the present invention can be used to produce a modified fluororesin molded product having desired functionality such as PTFE, which has excellent adhesiveness to other materials. , The usage of fluororesin can be expanded.

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Abstract

L'invention fournit un nouveau modificateur de résine fluorée qui permet de modifier un corps moulé de résine fluorée.　Le modificateur de résine fluorée de l'invention comprend un copolymère séquencé qui contient : une unité constitutive (A) possédant un groupe alkyle d'au moins huit atomes de carbone sur une chaîne latérale, et dérivée d'un monomère arbitraire (A) choisi dans un groupe constitué d'un (méth)acrylate, d'un (méth)acrylamide, d'un éther vinylique, d'un ester vinylique, d'un siloxane, d'une αoléfine et d'un styrène substitué ; et une unité constitutive (B) dérivée d'un monomère (B) possédant un groupe polaire.
PCT/JP2020/023694 2019-07-22 2020-06-17 Modificateur de résine fluorée, et corps moulé de résine fluorée modifié ainsi que procédé de fabrication de celui-ci WO2021014836A1 (fr)

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Citations (3)

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JP2015229725A (ja) * 2014-06-05 2015-12-21 学校法人福岡大学 表面修飾材料、表面修飾用組成物、及び復元方法
JP2016209879A (ja) * 2011-01-21 2016-12-15 学校法人福岡大学 分散剤，分散体，分散体の粘度の調整方法，可動装置，表面処理剤，電解液，セパレータ，およびリチウムイオン二次電池
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JP2016209879A (ja) * 2011-01-21 2016-12-15 学校法人福岡大学 分散剤，分散体，分散体の粘度の調整方法，可動装置，表面処理剤，電解液，セパレータ，およびリチウムイオン二次電池
JP2015229725A (ja) * 2014-06-05 2015-12-21 学校法人福岡大学 表面修飾材料、表面修飾用組成物、及び復元方法
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