WO2013180236A1 - Procédé de fabrication d'un liquide de dispersion aqueux à teneur en polymère fluoré - Google Patents

Procédé de fabrication d'un liquide de dispersion aqueux à teneur en polymère fluoré Download PDF

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Publication number
WO2013180236A1
WO2013180236A1 PCT/JP2013/065084 JP2013065084W WO2013180236A1 WO 2013180236 A1 WO2013180236 A1 WO 2013180236A1 JP 2013065084 W JP2013065084 W JP 2013065084W WO 2013180236 A1 WO2013180236 A1 WO 2013180236A1
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group
fluoropolymer
aqueous
polyoxyethylene alkyl
monomer
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PCT/JP2013/065084
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English (en)
Japanese (ja)
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増田　祥
鷲見　直子
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旭硝子株式会社
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Priority to JP2014518732A priority Critical patent/JPWO2013180236A1/ja
Priority to CN201380028333.9A priority patent/CN104364281A/zh
Publication of WO2013180236A1 publication Critical patent/WO2013180236A1/fr

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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
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
    • C08F214/267—Tetrafluoroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/24—Trifluorochloroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/24—Trifluorochloroethene
    • C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
    • C08F214/247—Trifluorochloroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers

Definitions

  • the present invention relates to a method for producing a fluoropolymer aqueous dispersion. More specifically, the present invention relates to a method for producing an aqueous fluoropolymer dispersion in which polymerization is performed in the presence of a polyoxyethylene alkyl ether having a specific structure, which is excellent in storage stability and the resulting coating film is excellent in water resistance.
  • Patent Document 2 discloses a method for obtaining a fluoropolymer aqueous dispersion in which the above-mentioned problems are solved by emulsion polymerization in the presence of a nonionic emulsifier having a specific HLB (hydrophilic lipophilic balance value).
  • HLB hydrophilic lipophilic balance value
  • An object of the present invention is to provide a method for producing an aqueous fluoropolymer dispersion having excellent long-term storage stability and excellent water resistance.
  • the present inventors have obtained a monomer mixture containing a fluoroolefin and a hydrophilic macromonomer, an aqueous medium, a specific polyoxyethylene alkyl ether, and radical polymerization initiation.
  • the long-term storage stability of the aqueous fluoropolymer dispersion, and the water resistance of the coating film obtained using the aqueous dispersion is improved by performing polymerization in the presence of an agent.
  • the present invention has the following gist.
  • X represents a radically polymerizable unsaturated group
  • Y represents a divalent linking group containing an alicyclic group
  • Z represents a hydrophilic site having a polyoxyalkylene chain.
  • ⁇ 2> The method for producing an aqueous fluoropolymer dispersion according to ⁇ 1>, wherein the aqueous medium is ion-exchanged water.
  • ⁇ 3> The method for producing an aqueous fluoropolymer dispersion according to ⁇ 1> or ⁇ 2>, wherein the fluoroolefin is chlorotrifluoroethylene or tetrafluoroethylene.
  • ⁇ 4> The method for producing an aqueous fluoropolymer dispersion according to any one of ⁇ 1> to ⁇ 3>, wherein the radical polymerization initiator is a water-soluble radical initiator.
  • Q (OCH 2 CH 2 ) n —O—R 1 (2)
  • Q is any one of a hydrogen atom, a methyl group and an ethyl group, R 1 is a linear alkyl group having 10 to 14 carbon atoms, and n is an integer of 9 to 11
  • n is an integer of 9 to 11
  • Q is a hydrogen atom
  • R 1 is a linear alkyl group having 11 to 12 carbon atoms
  • n is 9 to 10.
  • ⁇ 7> The fluorine-containing polymer according to any one of the above ⁇ 1> to ⁇ 6>, wherein the content of the total polyoxyethylene alkyl ether is 0.1 to 5 parts by mass with respect to 100 parts by mass of the monomer mixture
  • ⁇ 8> The aqueous fluoropolymer dispersion according to any one of ⁇ 1> to ⁇ 7>, wherein the hydrophilic macromonomer represented by the formula (1) is a monomer represented by the following formula (3): Manufacturing method. CH 2 ⁇ CH—Y— (CH 2 CH 2 O) m H (3) (In Formula (3), Y represents a divalent linking group containing an alicyclic group, and m is an integer of 2 to 40.)
  • the monomer mixture contains 20 to 80 mol% of the fluoroolefin and 0.1 to 25 mol% of the hydrophilic macromonomer,
  • the ratio of the repeating unit based on the fluoroolefin is 20 to 80 mol% with respect to all the repeating units in the fluoropolymer, and the ratio of the repeating unit based on the hydrophilic macromonomer is 0%.
  • the monomer mixture further includes a monomer having a crosslinkable group
  • the method for producing an aqueous fluoropolymer dispersion according to the present invention can provide an aqueous fluoropolymer dispersion having excellent long-term storage stability. Moreover, the coating film formed using it becomes excellent in water resistance.
  • the method for producing an aqueous fluoropolymer dispersion of the present invention comprises a fluoroolefin and the following formula (in the presence of an aqueous medium, a polyoxyethylene alkyl ether having an HLB value of 12 to 15 and a radical polymerization initiator ( 1) polymerizing a monomer mixture containing a hydrophilic macromonomer represented by
  • the polyoxyethylene alkyl ether is a polyoxyethylene alkyl ether whose alkyl group is a linear alkyl group (hereinafter also referred to as “linear alkyl group-containing polyoxyethylene alkyl ether”) with respect to all the polyoxyethylene alkyl ethers.
  • XYZ (1) (In Formula (1), X represents a radically polymerizable unsaturated group, Y represents a divalent linking group containing an alicyclic group, and Z represents a hydrophilic site having a polyoxyalkylene chain.)
  • the aqueous fluoropolymer dispersion in the present invention comprises a monomer mixture comprising a raw material fluoroolefin and the hydrophilic macromonomer represented by the above formula (1), an aqueous medium, a specific polyoxyethylene alkyl ether, A fluorine-containing polymer obtained by polymerization in the presence of a radical polymerization initiator is dispersed in an aqueous medium.
  • the fluoroolefin is preferably a fluoroolefin having 2 to 4 carbon atoms such as chlorotrifluoroethylene, tetrafluoroethylene, pentafluoropropylene, hexafluoropropylene, vinylidene fluoride or trifluoroethylene.
  • chlorotrifluoroethylene and tetrafluoroethylene are particularly preferable.
  • the hydrophilic macromonomer in the present invention is a monomer represented by the above formula (1).
  • the hydrophilic macromonomer represented by the above formula (1) as a raw material component of the fluoropolymer, not only the stability of the fluoropolymer aqueous dispersion is increased, but also the coating film obtained by using this Water resistance and the like are also improved.
  • the monomer represented by the formula (1) is a hydrophilic macromonomer having a hydrophilic portion having a polyoxyalkylene chain.
  • the macromonomer refers to a low molecular weight polymer or oligomer having a radical polymerizable unsaturated group at one end. That is, “a hydrophilic macromonomer having a hydrophilic moiety having a polyoxyalkylene chain” is a compound having a radical polymerizable unsaturated group at one end and having at least two repeating units of oxyalkylene in the monomer. is there. Although different depending on the type of repeating unit, those having 100 or less repeating units are usually preferably employed from the viewpoint of polymerizability and water resistance.
  • X in the above formula (1) is a radically polymerizable unsaturated group.
  • X is not particularly limited as long as it has a radical-polymerizable unsaturated bond, but specifically, a vinyl group and an allyl group are preferred, and the alternating copolymerization with a fluoroolefin is good. A vinyl group is more preferable.
  • Z in the above formula (1) is a hydrophilic portion having a polyoxyalkylene chain.
  • the hydrophilic site having a polyoxyalkylene chain is preferably a hydrophilic site such as a polyoxymethylene group, a polyoxyethylene group, or a polyoxypropylene group.
  • the number of repeating units of the alkylene chain is preferably 12 to 40, more preferably 13 to 30, and still more preferably 13 to 18.
  • the end of the polyoxyalkylene chain may be a hydroxyl group, an ionic group such as a carboxy group, or an alkyl group such as a methyl group, an ethyl group, or a propyl group.
  • the stability of the resulting fluoropolymer aqueous dispersion is stable. A hydroxyl group is more preferred because it is good.
  • the hydrophilic macromonomer having a hydrophilic portion having a polyoxyalkylene chain for example, W (OCH 2 ) a- (OCH 2 CH 2 ) b- ( OCH 2 CH (CH 3 )) c- moiety
  • W is a hydrogen atom, a methyl group or an ethyl group
  • a, b and c are each an integer of 0 to 40 (where a + b + c is 2 to 40)
  • a monomer having a formula (1) corresponding to Z in the above formula (1) for example, W (OCH 2 ) a- (OCH 2 CH 2 ) b- ( OCH 2 CH (CH 3 )) c- moiety
  • W is a hydrogen atom, a methyl group or an ethyl group
  • a, b and c are each an integer of 0 to 40 (where a + b + c is 2 to 40)
  • hydrophilic portion having a nonionic polyoxyalkylene chain Z in the above formula (1)
  • a portion represented by H (OCH2CH2) m- m is an integer of 2 to 40) is more preferred.
  • a monomer represented by the following formula (3) is more preferable.
  • Y represents a divalent linking group having an alicyclic group, and m is an integer of 2 to 40.
  • Y in the above formula (1) is a divalent linking group having an alicyclic group.
  • a cyclohexylene group is preferable.
  • the position of the bond of the cyclohexylene group in Y is not limited to any of 1, 1-position, 1, 2-position, 1, 3-position, 1, 4-position, but the stability of the resulting fluoropolymer aqueous dispersion Therefore, the 1st and 4th positions are preferable.
  • the group bonded to the alicyclic group in Y is preferably a divalent saturated hydrocarbon group, a divalent saturated hydrocarbon group having an etheric oxygen atom, or the like, and a divalent saturated hydrocarbon group having an etheric oxygen atom. Is more preferable.
  • Examples of the divalent saturated hydrocarbon group having an etheric oxygen atom in Y include an oxomethylene group, an oxodimethylmethylene group, and an oxoethylene group, and an oxomethylene group is more preferable.
  • examples of the hydrophilic macromonomer include monomers represented by the following formulas (4) to (7), and monomers represented by the following formulas (4) and (5) are more preferable. Since the monomer represented by the following formula (4) having a vinyl ether structure is excellent in copolymerizability with a fluoroolefin, it is particularly preferable.
  • the hydrophilic macromonomer in the present invention is produced by a known method such as polymerization of formaldehyde or diol, or ring-opening polymerization of a compound having an alkylene oxide or a lactone ring to a vinyl ether having a hydroxyl group or an allyl ether having a hydroxyl group. Is possible. It can also be produced by the method described in Japanese Patent Application Laid-Open No. 7-053646.
  • a polymer having a condensable functional group is produced by radical polymerization of an ethylenically unsaturated monomer having a hydrophilic group in the presence of an initiator having a condensable functional group and a chain transfer agent,
  • a method in which a compound such as glycidyl vinyl ether or glycidyl allyl ether is reacted with the functional group of this polymer to introduce a radical polymerizable unsaturated group at the terminal is exemplified.
  • the aqueous fluoropolymer dispersion in the present invention is obtained by polymerizing a monomer mixture containing a fluoroolefin and a hydrophilic macromonomer represented by the above formula (1).
  • the fluoroolefin-based repeating unit and the above formula (1) Containing a fluorine-containing polymer whose essential component is a repeating unit based on a hydrophilic macromonomer.
  • the fluorine-containing polymer has a repeating unit based on a monomer other than the fluoroolefin and the hydrophilic macromonomer represented by the above formula (1) (hereinafter also referred to as “other repeating unit”). Is preferred.
  • other repeating unit a monomer other than the fluoroolefin and the hydrophilic macromonomer represented by the above formula (1)
  • Examples of monomers other than the fluoroolefin and the hydrophilic macromonomer represented by the following formula (1) include monomers having a crosslinkable group and monomers having no crosslinkable group. During the polymerization, by adding these monomers to the monomer mixture and performing the polymerization, it is possible to introduce repeating units based on these monomers (other repeating units).
  • the monomer having a crosslinkable group is a monomer having neither a fluorine atom nor a polyoxyalkylene chain and having a crosslinkable group.
  • the monomer having no crosslinkable group is a monomer that does not contain any of a fluorine atom, a polyoxyalkylene chain, and a crosslinkable group.
  • crosslinkable group in the monomer having a crosslinkable group examples include a hydroxyl group, a carboxy group, an amino group, an epoxy group, and a hydrazine residue, and a hydroxyl group is more preferable.
  • Examples of monomers having a hydroxyl group as a crosslinkable group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2 -Hydroxyalkyl vinyl ethers such as methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexanedimethanol monovinyl ether; Ethylene glycol monovinyl ethers such as diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether;
  • Hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 3-hydroxypropyl allyl ether, 4-hydroxybutyl allyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether; Hydroxyalkylcarboxylic acid vinyl esters such as 2-hydroxypropanoic acid vinyl ester and 4-hydroxypentanoic acid vinyl ester; Hydroxyalkylcarboxylic acid allyl esters such as 2-hydroxypropanoic acid allyl ester and 4-hydroxypentanoic acid allyl ester; And (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate.
  • a method for introducing a repeating unit based on a monomer having a hydroxyl group into the fluoropolymer includes, in addition to the method of copolymerizing a monomer having a hydroxyl group, a hydroxyl group after polymerization.
  • Monomers having a carboxy group as a crosslinkable group include 3-butenoic acid, 4-pentenoic acid, 2-hexenoic acid, 3-hexenoic acid, 5-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, and 6-heptene.
  • Acid 3-octenoic acid, 7-octenoic acid, 2-nonenoic acid, 3-nonenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, cinnamon Unsaturated carboxylic acids such as acids; Saturated carboxylic acid vinyl ethers such as vinyloxyvaleric acid, 3-vinyloxypropionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid, 3- (2-vinyloxyethoxycarbonyl) propionic acid, and the like;
  • Saturated carboxylic acid allyl ethers such as allyloxyvaleric acid, 3-allyloxypropionic acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid;
  • Saturated polyvalent carboxylic acid monovinyl esters such as monovinyl adipate, monovinyl succinate, vinyl phthalate, vinyl pyromellitic acid;
  • Unsaturated dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, or intramolecular acid anhydrides thereof;
  • unsaturated dicarboxylic acid monoalkyl esters such as itaconic acid monomethyl ester, maleic acid monomethyl ester, and fumaric acid monomethyl ester.
  • a method for introducing a repeating unit based on a monomer having a carboxy group includes dibasic acid anhydride after polymerization of a fluoropolymer having a hydroxyl group. There is a method of forming a carboxy group by reaction.
  • Examples of monomers having an epoxy group as a crosslinkable group include epoxy group-containing alkyl vinyl ethers such as glycidyl vinyl ether; epoxy group-containing alkyl allyl ethers such as glycidyl allyl ether; epoxy group-containing alkyl acrylates or methacrylates such as glycidyl acrylate and glycidyl methacrylate. And the like.
  • the hydrazine residue is prepared by preparing a fluorine-containing polymer having a carbonyl group, and then dicarboxylic acid dihydrazide (for example, isophthalic acid dihydrazide, adipic acid dihydrazide) or hydrazine hydrate in an amount of 0.02 to 1 mol relative to 1 mol of the carbonyl group. It is obtained by blending and reacting by heating.
  • dicarboxylic acid dihydrazide for example, isophthalic acid dihydrazide, adipic acid dihydrazide
  • hydrazine hydrate in an amount of 0.02 to 1 mol relative to 1 mol of the carbonyl group. It is obtained by blending and reacting by heating.
  • the fluoropolymer in the present invention has a repeating unit based on a monomer having a crosslinkable group, it becomes possible to crosslink when the fluoropolymer aqueous dispersion of the present invention is used as a
  • Monomers having no crosslinkable group include olefins such as ethylene and propylene; vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; vinyl esters such as vinyl butanoate and vinyl octoate.
  • olefins such as ethylene and propylene
  • vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether
  • vinyl esters such as vinyl butanoate and vinyl octoate.
  • Aromatic vinyl compounds such as styrene and vinyl toluene
  • vinyl compounds such as Allyl ethers such as ethyl allyl ether
  • examples thereof include acryloyl compounds such as butyl acrylate; acrylic est
  • the fluoropolymer in the present invention has a repeating unit based on a monomer having no crosslinkable group
  • the fluoropolymer aqueous dispersion of the present invention is used as a coating, the coating film is given flexibility and the like. Is possible.
  • the content ratio of the repeating units based on fluoroolefin in the fluoropolymer in the present invention is preferably from 20 to 80 mol%, more preferably from 30 to 70 mol%, based on all repeating units in the fluoropolymer.
  • the repeating unit based on the fluoroolefin is in the above range, the weather resistance is sufficiently exhibited and the water dispersibility is also good.
  • the monomer mixture may be polymerized using 20 to 80 mol% of the fluoroolefin.
  • the content of the repeating unit based on the hydrophilic macromonomer is preferably 0.1 to 25 mol%, more preferably 0.3 to 5 mol%, based on all repeating units in the fluoropolymer. If the repeating unit based on the hydrophilic macromonomer is in the above range, the water dispersibility is good, and the weather resistance and water resistance of the coating film are also good.
  • the monomer mixture may be polymerized using 0.1 to 25 mol% of the hydrophilic macromonomer. Good.
  • the content of the repeating unit is preferably from 0.1 to 25 mol% based on all repeating units in the fluoropolymer. More preferred is ⁇ 15 mol%. If the ratio of this unit is the above range, water dispersibility is good. Further, when the coating film is cured, it has an appropriate flexibility, and the water resistance is not lowered due to the influence of the remaining crosslinkable group.
  • the monomer mixture may be polymerized using 1 to 15 mol% of a monomer having a crosslinkable group.
  • the repeating unit based on the hydrophilic macromonomer includes one having a hydroxyl group
  • the repeating unit acts as a crosslinkable site, and thus is calculated as the content of the repeating unit based on the monomer having a crosslinkable group. To be included.
  • the content of the repeating unit other than the repeating unit based on the monomer having no crosslinkable group that is, the repeating unit based on fluoroolefin, the repeating unit based on the hydrophilic macromonomer and the repeating unit having a crosslinkable group is fluorine-containing. 20 to 80 mol% is preferable with respect to all repeating units in the polymer, and 40 to 60 mol% is more preferable. This is because sufficient weather resistance is exhibited.
  • a fluoroolefin and a hydrophilic macromonomer and a monomer having a crosslinkable group and / or a crosslinkable group, which are added as necessary, are raw material components of the fluoropolymer.
  • a monomer mixture containing a monomer or the like that does not have is polymerized in the presence of an aqueous medium, a polyoxyethylene alkyl ether having an HLB value of 12 to 15, and a radical polymerization initiator.
  • polyoxyethylene alkyl ether having an HLB value of 12 to 15 will be described.
  • the HLB value is a hydrophilic / lipophilic balance value.
  • the calculated value by the Griffin method is generally used.
  • HLB 20 ⁇ sum of formula weight of hydrophilic part / molecular weight
  • the polyoxyethylene alkyl ether has an HLB value of 12 to 15, preferably 13 to 15.
  • polyoxyethylene alkyl ether having an HLB value of 12 to 15 is converted to polyoxyethylene alkyl ether containing linear alkyl group. 60 to 100 mol% of the amount. If the proportion of the linear alkyl group-containing polyoxyethylene alkyl ether in the total polyoxyethylene alkyl ether is within this range, the polymerization proceeds stably, and the stability of the resulting fluoropolymer aqueous dispersion increases, And the water resistance of the coating film obtained from this fluoropolymer aqueous dispersion liquid also becomes favorable.
  • polyoxyethylene alkyl ether is a nonionic emulsifier and forms micelles during polymerization. At that time, it is considered that when the ratio of the alkyl group in the polyoxyethylene alkyl ether is a linear alkyl group is high, stable micelles are formed.
  • the amount of total polyoxyethylene alkyl ether added during polymerization can be reduced, the remaining amount in the resulting coating film is reduced, and the resulting coating film It is considered that water resistance is improved.
  • a polyoxyethylene alkyl ether containing 60 to 100 mol% of a linear alkyl group-containing polyoxyethylene alkyl ether with respect to the total polyoxyethylene alkyl ether can be added in an amount of 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of the monomer mixture. More preferably, it is 1 to 5 parts by mass.
  • polyoxyethylene alkyl ether containing 60 to 100 mol% of linear alkyl group-containing polyoxyethylene alkyl ether means that 0 to 40 mol% of other polyoxyethylene alkyl ethers are contained.
  • the alkyl group may be a branched alkyl group, a cyclic alkyl group or a mixture.
  • the polyoxyethylene alkyl ether may have a fluorine atom, but preferably has no fluorine atom. That is, non-fluorinated polyoxyethylene alkyl ether is preferable.
  • the linear alkyl group-containing polyoxyethylene alkyl ether in the present invention preferably has a structure represented by the following formula (2).
  • Q (OCH 2 CH 2 ) n —O—R 1 (2)
  • Q is a hydrogen atom, a methyl group or an ethyl group
  • R 1 is a linear alkyl group having 10 to 14 carbon atoms
  • n is an integer of 9 to 11
  • Q is a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • the carbon number of the linear alkyl group of R 1 of the linear alkyl group-containing polyoxyethylene alkyl ether represented by the formula (2) is 10 to 14 are preferable, and 11 to 12 are more preferable.
  • N is preferably an integer of 9 to 11, more preferably an integer of 9 to 10. Since the HLB value is the value of all polyoxyethylene alkyl ethers, the number of carbon atoms of the polyoxyethylene alkyl ether other than the linear alkyl group-containing polyoxyethylene alkyl ether is also the same as that of the linear alkyl group-containing polyoxyethylene.
  • the number of repeating units at the oxyethylene site is preferably 9 to 11, more preferably 9 to 10.
  • the HLB value is a balance between hydrophilicity and lipophilicity, the number of carbon atoms of the alkyl group of the polyoxyethylene alkyl ether and the number of repeating units of the hydrophilic group, that is, ethylene oxide group (linear alkyl group-containing polyoxyethylene alkyl) In ether, it is considered that it is passively determined by the number of carbon atoms of R 1 represented by the above formula (2) and the number of moles of ethylene oxide groups added in the above formula (2).
  • the HLB value depends on the number of carbons of the alkyl group of the polyoxyethylene alkyl ether, the hydrophilic group, etc. Will fluctuate.
  • the total polyoxyethylene alkyl ether has an HLB value of 12 to 15, and the polyoxyethylene alkyl ether contains 60 to 100 mol% of a linear alkyl group-containing polyoxyethylene alkyl ether.
  • the proportion of the polyoxyethylene alkyl ether containing a linear alkyl group in the polyoxyethylene alkyl ether is determined as follows.
  • Straight chain ratio (number of moles of polyoxyethylene alkyl ether having a straight chain alkyl group) / (number of moles of total polyoxyethylene alkyl ether) ⁇ 100
  • Polyoxyethylene alkyl ether is usually produced from higher alcohol as a raw material.
  • a proportion having a branched alkyl group or a cyclic alkyl group as a higher alcohol used as a raw material A low alcohol may be used.
  • the proportion of the linear alkyl group-containing polyoxyethylene alkyl ether in the obtained polyoxyethylene alkyl ether is approximately 100. %, And the ratio decreases with synthetic alcohol.
  • synthetic alcohols when the Ziegler method is used, the proportion of linear alkyl groups is high.
  • Newcol N-1110 As a commercial product of polyoxyethylene alkyl ether having an HLB value of 12 to 15 and containing 60 to 100 mol% of a linear alkyl group-containing polyoxyethylene alkyl ether, Newcol N-1110 (HLB value: 14. 2, content of linear lauryl group-containing polyoxyethylene alkyl ether: 60 mol%, manufactured by Nippon Emulsifier Co., Ltd.).
  • Examples of the aqueous medium in the method for producing an aqueous dispersion of a fluoropolymer of the present invention include ion-exchanged water. If necessary, a water-soluble organic medium can be used in combination with ion-exchanged water. In addition, what is necessary is just to adjust the quantity of an aqueous medium suitably so that it may become below a critical micelle density
  • the initiation of the polymerization reaction in the method for producing an aqueous dispersion of a fluorine-containing polymer of the present invention is carried out by adding a radical polymerization initiator in the same manner as in the usual radical polymerization.
  • a radical polymerization initiator a normal radical initiator can be used, but a water-soluble radical initiator is preferable.
  • water-soluble radical initiators include persulfates such as ammonium persulfate and potassium persulfate, dibasic peroxides such as hydrogen peroxide, disuccinic acid peroxide, and diglutaric acid peroxide, and azobisisobutylamidine hydrochloride. And azobisisobutyronitrile. Of these, ammonium persulfate and potassium persulfate are preferably used. Or a redox initiator consisting of a combination of these with a reducing agent such as sodium hydrogen sulfite and sodium thiosulfate, and a redox agent coexisting with a small amount of iron, ferrous salt, silver sulfate, etc. are also possible. It is.
  • the amount of radical polymerization initiator used can be appropriately changed according to the type, polymerization conditions, etc., but is usually preferably 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of the monomer mixture used for the polymerization. 0.01 to 0.3 parts by mass is more preferable.
  • These radical polymerization initiators may be added all at once, but may be added in portions or sequentially as necessary.
  • a pH adjusting agent may be used for the purpose of adjusting the pH of the polymerization system.
  • pH adjusters that can be used in the present invention include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen orthophosphate, sodium thiosulfate, and sodium tetraborate, and triethylamine, triethanolamine, dimethylethanolamine, diethylethanolamine, and the like.
  • Organic bases and the like are exemplified.
  • the addition amount of the pH adjuster is usually 0.05 to 2 parts by mass, preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the aqueous medium.
  • the higher the pH the faster the polymerization rate tends to be. Therefore, it is preferable to increase the pH with a pH adjuster.
  • the optimum polymerization starting temperature is appropriately selected according to the type of radical polymerization initiator, but it is usually preferably 0 to 100 ° C., particularly preferably about 10 to 90 ° C.
  • the reaction pressure can be appropriately selected, but it is usually desirable to employ 1 to 100 kg / cm 2 , particularly about 2 to 50 kg / cm 2 .
  • a monomer mixture as a raw material component, an aqueous medium, the polyoxyethylene alkyl ether, a radical initiator and the like may be charged all at once and polymerized.
  • a stirrer such as a homogenizer before adding the radical polymerization initiator, in order to reduce the particle size of the dispersed particles and improve various properties such as the stability of the aqueous dispersion and the gloss of the resulting coating film.
  • the monomer mixture may be added in portions or continuously. At that time, the monomer composition in the monomer mixture may be different.
  • the fluoropolymer aqueous dispersion in the present invention can be used as it is or as an aqueous coating, but if necessary, a colorant, a plasticizer, an ultraviolet absorber, a leveling agent, a repellency inhibitor, An anti-burr agent, a curing agent and the like may be mixed.
  • a colorant include dyes, organic pigments, and inorganic pigments.
  • plasticizer examples include known ones such as low molecular weight plasticizers such as dioctyl phthalate, high molecular weight plasticizers such as vinyl polymer plasticizers, and polyester plasticizers.
  • the curing agent examples include blocked isocyanates such as hexamethylene isocyanate trimer or emulsion dispersions thereof, melamine resins such as methylated melamine, methylolated melamine, and butyrololized melamine, and urea resins such as methylated urea and butylated urea. Can be mentioned.
  • blocked isocyanates such as hexamethylene isocyanate trimer or emulsion dispersions thereof
  • melamine resins such as methylated melamine, methylolated melamine, and butyrololized melamine
  • urea resins such as methylated urea and butylated urea.
  • HLB The HLB of the polyoxyethylene alkyl ether was measured as described above. Specifically, it calculated using the calculation method by the Griffin method.
  • Example 1 In an autoclave with a stainless steel stirrer with an internal volume of 2500 ml, a fluoropolymer was synthesized using the raw material components in the number of parts shown in Table 1.
  • CTFE chlorotrifluoroethylene
  • 2-ethylhexyl vinyl ether (2-EHVE)
  • CHMVE cyclohexanedimethanol monovinyl ether
  • CMEOVE hydrophilic macromonomer
  • 928 g of ion-exchanged water 3 g of potassium carbonate (K 2 CO 3 )
  • polyoxyethylene lauryl ether A manufactured by Nippon Emulsifier Co., Ltd., product name: New Coal N-1110, HLB value: 14.2, linear lauryl group-containing poly Oxyethylene alkyl ether content: 60 mol%) 52 g and sodium lauryl sulfate 1 g were charged, cooled to 20 ° C. or lower, pressurized with nitrogen gas to 0.7 MPa, and degassed.
  • the said hydrophilic macromonomer (CMEOVE) is a compound shown by following formula (8), The number average molecular weight of this hydrophilic macromonomer is about 850.
  • CH 2 CHOCH 2 CH-cHex-CH 2 (OCH 2 CH 2 ) x OH (8) (In the formula, cHex represents a cyclohexyl group, and x is a value at which the number average molecular weight of the compound is about 850.)
  • Example 2 instead of polyoxyethylene lauryl ether A, polyoxyethylene lauryl ether B (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: DKS NL-100, HLB value: 13.8, linear lauryl group-containing polyoxyethylene alkyl ether) (Content: 100 mol%)
  • a fluoropolymer aqueous dispersion (b) having a solid concentration of 50% by mass was obtained in the same manner as in Example 1, except that 100 mol%) was used.
  • Fluoropolymer aqueous dispersions a and b obtained by polymerization using a polyoxyethylene lauryl ether having a linear lauryl group-containing polyoxyethylene alkyl ether content of 60% or more were tested for storage stability.
  • the amount of sediment in was less than in c.
  • the fluoropolymer aqueous dispersion c obtained by polymerization using polyoxyethylene lauryl ether having a linearity of lauryl group of less than 60% the sedimentation amount was larger than those of a and b.
  • test pieces a ′ and b ′ having a coating film formed using a coating composition obtained using a polyoxyethylene lauryl ether having a linearity of lauryl groups of 60% or more are water permeable Excellent in both properties and hardness.
  • the method for producing a fluoropolymer aqueous dispersion of the present invention can provide a fluoropolymer having excellent storage stability. Moreover, when the fluoropolymer aqueous dispersion obtained by the production method of the present invention forms a coating film, it can be a coating film having excellent water resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un liquide de dispersion aqueux à teneur en polymère fluoré qui a une excellente stabilité au stockage et est apte à fournir un film de revêtement qui a une excellente résistance à l'eau. Lorsqu'un mélange de monomère contenant une oléfine fluorée et un macromonomère hydrophile est polymérisé en présence d'un milieu aqueux, de polyoxyéthylène alkyl éthers et d'un amorceur de polymérisation par voie radicalaire, il y a des polyoxyéthylène alkyl éthers utilisés qui comprennent un polyoxyéthylène alkyl éther qui a une valeur HLB de 12-15 et dans lesquels le groupe alkyle est un groupe alkyle linéaire dans une quantité de 60-100 % en moles par rapport à la quantité totale des polyoxyéthylène alkyl éthers.
PCT/JP2013/065084 2012-06-01 2013-05-30 Procédé de fabrication d'un liquide de dispersion aqueux à teneur en polymère fluoré WO2013180236A1 (fr)

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WO2017122700A1 (fr) * 2016-01-14 2017-07-20 旭硝子株式会社 Dispersion aqueuse, son procédé de production, matériau de revêtement à base d'eau, et article revêtu
EP3345938A4 (fr) * 2015-09-01 2019-04-10 AGC Inc. Polymère contenant du fluor, procédé pour le produire, et produit durci de polymère contenant du fluor
US20220177689A1 (en) * 2019-03-29 2022-06-09 Kureha Corporation Vinylidene fluoride-based polymer composition obtained using non-fluorinated surfactant and production method therefor

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JPH0753646A (ja) * 1993-08-11 1995-02-28 Asahi Glass Co Ltd 含フッ素水性分散液
JPH11246611A (ja) * 1998-02-27 1999-09-14 Asahi Glass Co Ltd 含フッ素複合重合体微粒子の水性分散体
JP2000129195A (ja) * 1998-08-20 2000-05-09 Asahi Glass Co Ltd 含フッ素水性塗料組成物

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WO2006109854A1 (fr) * 2005-04-13 2006-10-19 Daikin Industries, Ltd. Procede de fabrication d’une dispersion aqueuse de fluoropolymere
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JPH05320533A (ja) * 1992-05-25 1993-12-03 The Ink Tec Kk 易分散性粉末顔料の製造方法
JPH0753646A (ja) * 1993-08-11 1995-02-28 Asahi Glass Co Ltd 含フッ素水性分散液
JPH11246611A (ja) * 1998-02-27 1999-09-14 Asahi Glass Co Ltd 含フッ素複合重合体微粒子の水性分散体
JP2000129195A (ja) * 1998-08-20 2000-05-09 Asahi Glass Co Ltd 含フッ素水性塗料組成物

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3345938A4 (fr) * 2015-09-01 2019-04-10 AGC Inc. Polymère contenant du fluor, procédé pour le produire, et produit durci de polymère contenant du fluor
WO2017122700A1 (fr) * 2016-01-14 2017-07-20 旭硝子株式会社 Dispersion aqueuse, son procédé de production, matériau de revêtement à base d'eau, et article revêtu
JPWO2017122700A1 (ja) * 2016-01-14 2018-11-22 Ａｇｃ株式会社 水性分散液、その製造方法、水性塗料および塗装物品
US20220177689A1 (en) * 2019-03-29 2022-06-09 Kureha Corporation Vinylidene fluoride-based polymer composition obtained using non-fluorinated surfactant and production method therefor
US12054605B2 (en) * 2019-03-29 2024-08-06 Kureha Corporation Vinylidene fluoride-based polymer composition obtained using non-fluorinated surfactant and production method therefor

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